CN109526217B

CN109526217B - Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof

Info

Publication number: CN109526217B
Application number: CN201880002860.5A
Authority: CN
Inventors: 黄庭; 郭子芳; 孙竹芳; 周俊领; 谢伦嘉; 杨红旭; 李秉毅; 苟清强; 黄廷杰; 寇鹏; 张晓帆; 付梅艳; 林洁; 马永华
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-07-19
Filing date: 2018-07-19
Publication date: 2022-05-24
Anticipated expiration: 2038-07-19
Also published as: KR20200033267A; US11401356B2; EP3656754B1; KR102336976B1; JP7038797B2; EP3656754A4; BR112020001201B1; WO2019015638A1; RU2740916C1; JP2020526655A; EP3656754A1; BR112020001201A2; ES2980848T3; US20200181296A1; FI3656754T3; CN109526217A

Abstract

A Ziegler-Natta type catalyst system for the polymerization of olefins is disclosed, comprising at least one compound of formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) both, wherein M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆' each independently selected from hydrogen, hydroxyl, amino, aldehyde group, carboxyl group, acyl group, halogen atom, -R₁OR-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁‑C₁₀A hydrocarbon group or a group selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, C₁‑C₁₀Alkoxy and heteroatom substituted C₁‑C₁₀A hydrocarbyl group; wherein when M is₁‑M₆And M₁’‑M₆Any two adjacent groups on the same phenyl ring in' are each independently selected from R₁and-OR₂When said two adjacent groups are optionally linked to form a ring, provided that M₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆Not both are hydrogen.

Description

Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives

CROSS-REFERENCE TO RELATED APPLICATIONS

The priority of the present application for chinese patent application nos. 201710591148.0, 201710591173.9, 201710592381.0, 201710592384.4, 201710592385.9, 201710592383.X, 201710591181.3, 201710591859.8, 201710591855.X, 201710592386.3, 201710592398.6, filed 2017, month 7, 19, said documents being incorporated by reference in their entirety and for all purposes in the present application.

Technical Field

The invention belongs to the field of olefin polymerization catalysts, and particularly relates to an olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof.

Background

In the field of olefin polymerization catalysts, there have been attempts to introduce various electron donors into olefin polymerization catalysts to improve one or more properties of the catalyst. For example, CN1958620A, CN1743347A, CN102295717A and CN103772536A teach introducing a siloxane electron donor, an o-alkoxy benzoate/carboxylic ester (or diether) compound electron donor, and a benzoate electron donor into the catalyst respectively, so as to improve the hydrogen response sensitivity of the catalyst. For another example, CN1726230A, CN1798774A and CN101050248A teach introducing electron donors such as alcohols, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers and aliphatic carboxylates into the catalyst to improve copolymerization performance of the catalyst. For another example, CN102807638A teaches to introduce a formulated long carbon chain monoester/short carbon chain monoester electron donor into the catalyst to improve the activity of the catalyst.

Cyclotriveratrole and some of its derivatives are known (see, e.g., Tetrahedron, Vol.43, No.24, pp.5725-5759,1987; China science B edition: chemistry 2009, Vol.39, phase 4: 329-342). However, the use of cyclotri-veratrum hydrocarbons and derivatives thereof in olefin polymerization catalysts has never been taught in the prior art.

Summary of The Invention

The inventor surprisingly found in the research process that: when the cyclotri-veratrum hydrocarbon and the derivative thereof are introduced into a solid catalyst component of an olefin polymerization catalyst system as an internal electron donor, the olefin polymerization catalyst can not only show good copolymerization performance and activity, but also show high polymerization activity and high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is more than or equal to 1.5); when the heteroatom-containing cyclotri-veratrum hydrocarbon and the derivatives thereof are introduced into an olefin polymerization catalyst system as an external electron donor, the catalyst system shows good copolymerization performance. Based on this finding, the present invention has been completed.

The invention provides an application of cyclotri veratrum hydrocarbon and a derivative thereof in an olefin polymerization catalyst, wherein the structure of the cyclotri veratrum hydrocarbon and the derivative thereof is shown as a formula (I):

wherein M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆' each independently selected from hydrogen, hydroxyl, amino, aldehyde group, carboxyl group, acyl group, halogen atom, -R₁OR-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁-C₁₀A hydrocarbon radical or a radical selected from the group consisting of hydroxy, amino, aldehyde, carboxyl, acyl, halogen atoms, C₁-C₁₀Alkoxy and heteroatom substituted C₁-C₁₀A hydrocarbyl group; wherein when M is₁-M₆And M₁’-M₆Any two of the' neighbors on the same benzene ringGroups such as M₁And M₁’，M₁And M₂，M₂And M₂’，M₃And M₃’，M₃And M₄，M₄And M₄’，M₅And M₅’，M₅And M₆，M₆And M₆' each is independently selected from R₁and-OR₂When the two adjacent groups are optionally linked to form a ring,

provided that M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆Not both are hydrogen.

In one embodiment, the cyclotri-veratrum hydrocarbon and derivatives thereof have the structure shown in formula (I'):

wherein M is₁、M₂、M₃、M₄、M₅And M₆Each independently selected from hydrogen, hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, -R₁and-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁-C₁₀A hydrocarbon group or a group selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, C₁-C₁₀Alkoxy and heteroatom substituted C₁-C₁₀A hydrocarbyl group, with the proviso that when two groups M adjacent to each other on the same phenyl ring are present₁And M₂Or M₃And M₄Or M₅And M₆Each independently selected from-R₁and-OR₂When said two adjacent groups are optionally linked to form a ring, and with the proviso that M is₁、M₂、M₃、M₄、M₅And M₆Not hydrogen at the same time.

In a second aspect, the present invention provides a catalyst system for olefin polymerization comprising at least one compound represented by formula (I) or formula (I') above as (I) an internal electron donor, (ii) an external electron donor, or (iii) both.

In a sub-aspect of the second aspect, the present invention provides a solid catalyst component for the polymerization of olefins, the solid catalyst component being at least one of the following solid catalyst components:

1) a solid catalyst component comprising magnesium, titanium, halogen and an internal electron donor compound, wherein said internal electron donor compound comprises at least one compound represented by formula (I) or formula (Γ) above;

2) a solid catalyst component comprising the reaction product of: a magnesium halide alcoholate, a titanium compound, an internal electron donor compound, and optionally an organoaluminum compound, wherein the internal electron donor compound comprises at least one compound represented by the above formula (I) or formula (I');

3) a solid catalyst component comprising the reaction product of: an alkoxy magnesium compound, a titanium compound and an internal electron donor compound, wherein the internal electron donor compound comprises at least one compound represented by the formula (I) or the formula (I');

4) a solid catalyst component comprising the reaction product of: the preparation method comprises the following steps of (1) carrying an ultrafine carrier with the particle size of 0.01-10 microns, magnesium halide, titanium halide and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor a and an internal electron donor b; the internal electron donor a is at least one compound represented by the formula (I) or the formula (I'); the internal electron donor b is selected from C₂-C₁₀Alkyl esters of saturated fatty carboxylic acids, C₇-C₁₀Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Fatty ethers, C₃-C₁₀Cyclic ether, C₃-C₁₀At least one of saturated aliphatic ketones;

5) a solid catalyst component comprising the reaction product of:

5-1) a liquid component containing magnesium selected from at least one of the following components:

alkyl radicalMagnesium or a solution thereof dispersed in a liquid hydrocarbon, the magnesium alkyl having the formula MgR₁R₂Wherein R is₁And R₂Each independently selected from substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, halogen atom, alkoxy and heteroatom;

② magnesium dihalides or magnesium dihalides in which one halogen atom is replaced by a group R₃OR OR₄The substituted derivative is dissolved in a solvent comprising an organophosphorus compound, an organic epoxy compound and optionally an alcohol compound R₅The product obtained in a solvent system of OH; and

③ using magnesium dihalide or magnesium dihalide molecular formula with one halogen atom being replaced by group R₃OR OR₄The substituted derivatives being dispersed in the alcoholic compound R₅Products obtained in OH;

wherein R is₃、R₄And R₅Each independently selected from substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, halogen atom, alkoxy or heteroatom;

5-2) a titanium compound;

5-3) an internal electron donor compound comprising at least one compound represented by the above formula (I) or formula (I');

optionally, 5-4) a precipitation aid selected from organic acid anhydride compounds and/or organosilicon compounds.

In another sub-aspect of the second aspect, the present invention provides an olefin polymerization catalyst comprising the reaction product of:

1) the above solid catalyst component;

2) cocatalysts, such as organoaluminum compounds; and

3) optionally an external electron donor compound.

1) a solid catalyst component comprising magnesium, titanium, halogen and optionally an internal electron donor compound;

2) cocatalysts, such as organoaluminum compounds; and

3) an external electron donor compound;

wherein the external electron donor compound comprises at least one compound represented by the above formula (I) or formula (I').

In some embodiments of this sub-aspect, the solid catalyst component comprises the reaction product of: a magnesium halide alcoholate, a titanium compound, an optional internal electron donor compound, and an optional organoaluminum compound; preferably, the organoaluminum compound has the formula AlR³ _aX³ _bH_cIn the formula, R³Is C₁-C₁₄A hydrocarbyl group; x³Is a halogen atom, preferably Cl, Br or I; a. b and c are each a number from 0 to 3, and a + b + c is 3.

In some embodiments of this sub-aspect, the solid catalyst component comprises the reaction product of: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound.

In some embodiments of this sub-aspect, the solid catalyst component comprises the reaction product of: superfine carrier, magnesium halide, titanium halide, internal electron donor b and optional internal electron donor a;

wherein the internal electron donor b is selected from C₂-C₁₀Alkyl esters of saturated fatty carboxylic acids, C₇-C₁₀Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Fatty ethers, C₃-C₁₀Cyclic ethers and C₃-C₁₀At least one of saturated aliphatic ketones; and

wherein the optional internal electron donor a is at least one compound of formula (I) or formula (I') above.

In some embodiments of this sub-aspect, the solid catalyst component comprises the reaction product of: the titanium-containing composite material comprises a magnesium-containing liquid component, a titanium compound, an optional internal electron donor compound and an optional auxiliary precipitator, wherein the auxiliary precipitator is selected from organic acid anhydride compounds and/or organic silicon compounds.

In a third aspect the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction.

A fourth aspect of the present invention provides an olefin polymerization process comprising: contacting an olefin monomer and optionally a comonomer with the olefin polymerization catalyst described above under polymerization conditions to form a polyolefin product, and recovering the polyolefin product. In some embodiments, the process comprises contacting ethylene and optionally a comonomer, such as a C3-C12 alpha-olefin, with the olefin polymerization catalyst described above under polymerization conditions to form a polyethylene product, and recovering the polyethylene product. In other embodiments, the process comprises contacting propylene and optionally a comonomer such as ethylene or a C4-C12 alpha-olefin with the olefin polymerization catalyst described above under polymerization conditions to form a polypropylene product, and recovering the polypropylene product.

A fifth aspect of the invention provides a polyolefin product, such as polyethylene or polypropylene, obtainable by the above-described olefin polymerization process.

According to the invention, the cyclotri-veratrum hydrocarbon and the derivative thereof shown in the formula (I)/(I') can be used as an internal electron donor and/or an external electron donor of a Ziegler-Natta type olefin polymerization catalyst. The introduction of cyclotri-veratrum hydrocarbons and derivatives thereof in olefin polymerization catalysts improves the properties of the resulting catalysts, such as activity, hydrogen sensitivity and copolymerization properties.

Description of The Preferred Embodiment

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

Definition of

As used herein, the terms "a," "an," and "the" are each intended to mean and include a plurality of the referenced item or object, unless specifically defined or stated otherwise herein, or unless the context clearly dictates otherwise.

All numerical values in the detailed description and claims herein are those indicated as modified by "about" or "approximately" and are considered subject to experimental error and variations, such as ± 10%, or ± 5%, or ± 2%, or ± 1%, as would be expected by a person of ordinary skill in the art.

For purposes of this disclosure and the appended claims, the olefin present in the polymer is the polymerized form of the olefin. Likewise, the use of the term polymer is intended to include homopolymers and copolymers, where copolymers include any polymer having two or more chemically distinct monomers.

The term "polyolefin" refers to polymers containing repeating units derived from olefins, for example polyalphaolefins such as polypropylene and/or polyethylene.

"Polypropylene" refers to polyolefins containing repeating propylene-derived units, including polypropylene homopolymers and polypropylene copolymers in which at least 50%, preferably at least 85% (by number) of the repeating units are derived from propylene monomers. Herein, polypropylene, propylene polymer, polypropylene polymer are used interchangeably.

"polyethylene" refers to polyolefins containing repeating ethylene-derived units, including polyethylene homopolymers and polyethylene copolymers in which at least 50%, preferably at least 85% (by number) of the repeating units are derived from ethylene monomer. Polyethylene, ethylene polymer, polyethylene polymer are used interchangeably herein.

"copolymer" means a polymer containing repeat units derived from at least two different monomers, preferably, for example, olefins such as ethylene, propylene, various butenes, and the like. Thus, the propylene copolymer or propylene-based polymer contains at least two different monomers, wherein more than 50%, preferably more than 85% (by number) of the repeating units are derived from propylene monomers.

"terpolymer" means a polymer containing repeating units derived from at least three different monomers, preferably, for example, olefins such as ethylene, propylene, various butenes, and the like. Thus, the propylene terpolymer contains at least three different monomers, wherein more than 50%, preferably more than 85% (by number) of the repeating units are derived from propylene monomers.

An "alkene" (alternatively referred to as an "alkene") is a straight-chain, branched, or cyclic compound of carbon and hydrogen having at least one double bond. An "alpha-olefin" is an olefin having a double bond in the alpha (or 1-) position.

Herein, "catalyst" and "catalyst system" are used interchangeably. A "catalyst" is a combination of at least one solid catalyst component, at least one co-catalyst, and optionally an external electron donor component. "polyolefin" catalysts are catalyst systems that can polymerize olefin monomers into polymers.

The term "hydrocarbyl" as used herein refers to a group having a structure that can be derived from a hydrocarbon by removing one or more hydrogens from the formula, and includes linear, branched, or cyclic alkyl, linear, branched, or cyclic alkenyl, linear, branched, or cyclic alkynyl, aryl, aralkyl, and alkaryl groups. The term "hydrocarbyl" as used herein, unless otherwise specified, generally refers to a hydrocarbyl group having 1 to 30, preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6 carbon atoms.

"alkyl" refers to a paraffinic hydrocarbon group that may be derived from an alkane by the removal of one or more hydrogens from the formula. The term "alkyl" as used herein, unless otherwise specified, generally refers to an alkyl group having 1 to 30, preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6 carbon atoms, such as methyl or ethyl, and the like. C₁-C₁₀Non-limiting examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

"alkenyl" refers to an olefinic hydrocarbon group that can be derived from an olefin by the removal of one or more hydrogens from the formula. The term "alkenyl" as used herein, unless otherwise indicated, generally refers to a group havingAlkenyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 6 carbon atoms. C₂-C₁₀Examples of alkenyl groups include, but are not limited to, ethenyl, propenyl, and allyl.

"alkynyl" refers to an acetylenic hydrocarbyl group that may be derived from an alkyne by the removal of one or more hydrogens from the formula. The term "alkynyl" as used herein, unless otherwise specified, generally refers to alkynyl groups having 2 to 30, preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 6 carbon atoms. C₂-C₁₀Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, and propargyl.

"aryl" refers to a group that can be derived from an aromatic hydrocarbon such as benzene, naphthalene, phenanthrene, anthracene, etc., e.g., phenyl or naphthyl, etc., by the removal of one or more hydrogens from the formula. C₆-C₁₀Examples of aryl groups include, but are not limited to, phenyl and naphthyl.

C₇-C₁₀Examples of alkylaryl groups include, but are not limited to, 4-methylphenyl and 4-ethylphenyl.

C₇-C₁₀Examples of arylalkyl groups include, but are not limited to, phenylmethyl, 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 2-dimethyl-2-phenyl-propyl, and 2-phenylpropyl.

The term "halogen atom" as used herein means F, Cl, Br or I, unless otherwise indicated.

The term "heteroatom" as used herein, unless otherwise indicated, refers to halogen atoms, O, N, S, P, Si, and B, and the like.

As used herein, unless otherwise indicated, the term "substituted C₁-C₁₀Hydrocarbyl "is generally referred to as" C₁-C₁₀The hydrogen atom (preferably one hydrogen atom) and/or the carbon atom on the hydrocarbon group "is substituted with a substituent. Preferably, the substituent is selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a hetero atom.

The term "amino" as used herein, unless otherwise indicated, refers to NR₁R₂Wherein R is₁And R₂Can be selected from hydrogen atoms or C₁-C₁₀The hydrocarbon group of (a) is,and R is₁And R₂May be the same or different.

In a first aspect, the present invention provides the use of cyclotri veratrum hydrocarbons and derivatives thereof of formula (i) in olefin polymerization catalysts:

wherein M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆' same or different, each selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R₁and-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁-C₁₀A hydrocarbon group or C substituted by a substituent selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a hetero atom₁-C₁₀A hydrocarbyl group; wherein when any two adjacent groups such as M are on the same phenyl ring₁And M₁’，M₁And M₂，M₂And M₂’，M₃And M₃’，M₃And M₄，M₄And M₄’，M₅And M₅’，M₅And M₆，M₆And M₆' each is independently selected from R₁and-OR₂When the adjacent two groups are optionally linked to form a ring,

Preferably, the cyclotri-veratrole hydrocarbon and derivatives thereof are represented by formula (I'):

wherein M is₁、M₂、M₃、M₄、M₅And M₆The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R₁and-OR₂Wherein R is₁And R₂Each independently is substituted or unsubstituted C₁-C₁₀A hydrocarbon group, the substituent being selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a hetero atom;

when two groups adjacent to each other on the same benzene ring are M₁And M₂Or M₃And M₄Or M₅And M₆Each independently selected from-R₁OR-OR₂When said two adjacent groups are optionally linked to each other to form a cyclic structure, with the proviso that M₁、M₂、M₃、M₄、M₅And M₆Not hydrogen at the same time.

According to the invention, C₁-C₁₀The hydrocarbyl group may be selected from C₁-C₁₀Alkyl radical, C₃-C₁₀Cycloalkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₆-C₁₀Aryl radical, C₇-C₁₀Alkylaryl and C₇-C₁₀Arylalkyl, and the like.

Preferably, in formula (I'), M₁、M₂、M₃、M₄、M₅And M₆Identical or different, each being selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a halogen atom, -R₁and-OR₂And R is₁And R₂Each independently selected from C substituted or unsubstituted by halogen atoms₁-C₁₀A hydrocarbyl group.

In some embodiments, M₁、M₃And M₅Are the same, and M₂、M₄And M₆The same is true.

In some embodiments, M₁、M₂、M₃、M₄、M₅And M₆The same is true.

In some preferred embodiments, the cyclotri-veratrum hydrocarbon and its derivatives are at least one selected from the group consisting of compounds represented by the following formula (i):

a compound A: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound B: m is a group of₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H

Compound C: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound D: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH(CH₃)₂，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound E: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound F: m₁＝M₃＝M₅＝OCH₃；M₂＝M₄＝M₆＝OCH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound G: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝OCH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound H: m is a group of₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝OCH₂CH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

A compound I: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OH，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound J: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝OH，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound K: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝NH₂，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound L: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝Cl，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound M: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝Br，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound N: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝I，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound O: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝CHO，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound P: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝OCH₂CH₂CH₂Br，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound Q: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₂Cl，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

A compound R: m₁＝M₃＝M₅＝OH，M₂＝M₄＝M₆＝OCH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

A compound S: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝Cl，M₂’＝M₃’＝M₄’＝M₅＝M₆＝H；

A compound T: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝M₃’＝Cl，M₂’＝M₄’＝M₅’＝M₆’＝H；

Compound U: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝M₃’＝M₅’＝Cl，M₂’＝M₄’＝M₆’＝H；

Compound V: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝M₃’＝M₆’＝Cl，M₂’＝M₄’＝M₅’＝H；

A compound W: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₃，M₁’＝M₃’＝M₅’＝NO₂，M₂’＝M₄’＝M₆’＝H。

In addition, when M₁＝M₃＝M₅＝X，M₂＝M₄＝M₆Y (X, Y denotes M as described above, respectively₁、M₃、M₅Optional groups and M₂、M₄、M₆Optional groups, and X is different from Y), the cyclotriveratrole and derivatives thereof represented by formula (I) may exist in the following isomers: m is a group of₁＝M₄＝M₅＝X，M₂＝M₃＝M₆＝Y；M₂＝M₄＝M₅＝X，M₁＝M₃＝M₆-Y; and/or M₂＝M₄＝M₆＝X，M₁＝M₃＝M₅-Y. Such isomers are also within the scope of the present invention.

Similarly, when M₁’＝M₃’＝M₅’＝X，M₂’＝M₄’＝M₆' Y (X, Y denotes M as described above, respectively₁’、M₃’、M₅' optional groups and M₂’、M₄’、M₆' optional group, and X is different from Y), the cyclotriveratrole hydrocarbon of formula (I) and its derivatives may exist in the following isomers: m₁’＝M₄’＝M₅’＝X，M₂’＝M₃’＝M₆’＝Y；M₂’＝M₄’＝M₅’＝X，M₁’＝M₃’＝M₆' -Y; and/or M₂’＝M₄’＝M₆’＝X，M₁’＝M₃’＝M₅' -Y. Such isomers are also within the scope of the present invention.

The cyclotri-veratrole hydrocarbon and derivatives thereof useful in the present invention may be prepared according to a method known per se. For example, the cyclotri-veratrole hydrocarbon and derivatives thereof may be prepared according to one of the following methods:

the method comprises the following steps: reacting a benzene derivative A shown in a formula (IV) with formaldehyde or a precursor thereof in the presence of an acidic substance and an optional halogenated hydrocarbon to obtain the cyclotri-veratrum hydrocarbon and the derivative thereof;

the second method comprises the following steps: in the presence of an acidic substance, catalyzing benzene derivative B shown in formula (V) to condense, thereby obtaining the cyclotri-veratrum hydrocarbon and derivatives thereof;

the third method comprises the following steps: catalyzing benzene derivative A shown in formula (IV) to react with formaldehyde or a precursor thereof in halogenated hydrocarbon in the presence of Lewis acid, so as to obtain the cyclotriveratryl hydrocarbon and the derivative thereof;

wherein M is₇、M₈、M₉、M₁₀Is as defined above for M in formula (I)₁-M₆The same definition is applied.

The acidic substance may be at least one selected from the group consisting of hydrochloric acid, perchloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, pyrosulfuric acid, sulfurous acid, phosphoric acid, pyrophosphoric acid, phosphorous acid, boric acid, formic acid, acetic acid, benzoic acid, trifluoroacetic acid, sulfonic acid, and benzenesulfonic acid.

The halogenated hydrocarbon may be at least one selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, methyl bromide, ethyl monochloride, propyl monochloride, butyl monochloride, pentane monochloride, hexane monochloride, ethyl bromide, 1, 2-dichloroethane, 1, 3-dichloropropane, 1, 4-dichlorobutane, 1, 5-dichloropentane, 1, 6-dichlorohexane, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, and benzene bromobenzene.

The lewis acid may be selected from at least one of boron trifluoride diethyl etherate, ferric trichloride, aluminum trichloride, and titanium tetrachloride.

The formaldehyde precursor may be selected from paraformaldehyde, for example trioxane.

In each of the above processes, the amount of each raw material may be selected with reference to conventional techniques, which are within the knowledge of those skilled in the art.

According to the application of the invention, the cyclotri-veratrum hydrocarbon and the derivative thereof in the formula (I) can be used as an internal electron donor compound in a solid catalyst component (main catalyst) of a Ziegler-Natta type olefin polymerization catalyst, or used as an external electron donor compound of the Ziegler-Natta type olefin polymerization catalyst, or used as both.

In the present invention, there is no particular limitation on the specific type of Ziegler-Natta type olefin polymerization catalyst to which the cyclotri-veratrum hydrocarbon of formula (I) and its derivative can be applied and the preparation method thereof. The present inventors have found that the cyclotri-veratrum hydrocarbons of formula (I) and derivatives thereof may be incorporated into various known Ziegler-Natta type olefin polymerization catalysts, for example as an alternative or supplement to the internal or external electron donor or both contained therein.

The first application of the first aspect of the present invention relates to the application of the cyclotri veratrum hydrocarbon of formula (I) and its derivatives as an internal electron donor compound in an olefin polymerization catalyst system, i.e., the cyclotri veratrum hydrocarbon of formula (I) and its derivatives are introduced into a solid catalyst component of the olefin polymerization catalyst system as a component of the solid catalyst component.

According to the first application, there are no particular restrictions on the specific type of the solid catalyst component into which the cyclotri-veratrum hydrocarbon of formula (I) and its derivatives are introduced, and the method of preparation thereof. The present inventors have found that the cyclotri-veratrum hydrocarbon of formula (I) and its derivatives can be incorporated as an internal electron donor component into various solid catalyst components known in the art for olefin polymerization. The olefin polymerization catalyst comprising the thus obtained solid catalyst component can not only exhibit good copolymerization properties and activities, but also exhibit high polymerization activities under conditions of high hydrogen-ethylene ratio (e.g., hydrogen partial pressure: ethylene partial pressure. gtoreq.1.5) and high polymer melt index.

In some embodiments of the first application, the olefin polymerization catalyst comprises the reaction product of:

1) a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor compound;

2) cocatalysts, for example organoaluminum compounds such as alkylaluminum compounds; and

3) an optional external electron donor component,

wherein the internal electron donor compound comprises at least one of the above-described cyclotris veratrole and derivatives thereof. In some embodiments, the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound, and an internal electron donor compound.

The magnesium compound and the titanium compound are those commonly used in the preparation of Ziegler-Natta type olefin polymerization catalysts.

Generally, the magnesium compound may be selected from at least one of magnesium halide, hydrate or alcoholate of magnesium halide, alkyl magnesium, and derivatives in which (at least one) halogen atom in the formula of magnesium halide is replaced with alkoxy group or haloalkoxy group.

The titanium compound may be represented by the following general formula: ti (OR)_nX’_4-nWherein R is C₁-C₈A hydrocarbon group, preferably C₁-C₈Alkyl, X' is a halogen atom such as fluorine, chlorine or bromine, 0. ltoreq. n.ltoreq.4. Preferably, the titaniumThe compound is at least one selected from titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium. More preferably, the titanium compound is titanium tetrachloride.

In a preferred embodiment, said solid catalyst component comprises said titanium compound and said cyclotri-veratrolene and derivatives thereof supported on a magnesium halide.

In still other embodiments, the solid catalyst component comprises the reaction product of an ultrafine support, a magnesium halide, a titanium halide, and an internal electron donor compound, wherein the ultrafine support has a particle size of 0.01 to 10 microns, and the ultrafine support may be selected from at least one of alumina, activated carbon, clay, silica, titania, magnesia, zirconia, polystyrene, and calcium carbonate.

In some embodiments, the molar ratio of cyclotri-veratrolene and derivatives thereof to magnesium (or magnesium compound) in the solid catalyst component is 0.0005-0.1: 1, preferably 0.001-0.1: 1, more preferably 0.002-0.05: 1.

In some embodiments, in the preparation of the catalyst component, the molar ratio of the titanium halide to the magnesium halide is from 1/20 to 1/2, the molar ratio of the titanium halide to the electron donor b is from 1/1 to 1/600, and the molar ratio of the titanium halide to the electron donor a is from 5/1 to 2000/1.

In some embodiments, the internal electron donor compound may further include other internal electron donors (hereinafter, referred to as internal electron donor b) conventionally used in the art other than the internal electron donor a, such as alcohols, organic acids, organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, amines, phosphate esters, amides, carbonates, phenols, pyridines, high molecular compounds having polar groups, and the like, in addition to the cyclotri-veratryl hydrocarbon and its derivatives (hereinafter, referred to as "internal electron donor a"). For example, the internal electron donor b may be selected from methyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl benzoate, ethyl p-methylbenzoate, methyl naphthoate, ethyl naphthoate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, butyl ether, tetrahydrofuran, 2-dimethyl-1, 3-diethoxypropane, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, organic epoxides (e.g., ethylene oxide, propylene oxide, epichlorohydrin, polyepichlorohydrin, polyethylene oxide), organic phosphorous compounds (e.g., trimethyl phosphate, triethyl phosphate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, dibutyl ether, tetrahydrofuran, 2-dimethyl-1, 3-diethoxypropane, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, organic epoxides (e.g., ethylene oxide, propylene oxide, epichlorohydrin, polyethylene oxide, trimethyl phosphate, triethyl phosphate, or a mixture of an organic phosphorous compound (e.g., methyl phosphate, triethyl phosphate, or a mixture of an organic phosphorous compound, a mixture of an organic phosphorous, a mixture of an organic group, a mixture of an organic phosphorous compound, a compound of an organic phosphorous compound, a mixture of an organic phosphorous compound, a type, at least one of tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate), polymethyl methacrylate, and polystyrene.

According to a first application, when an internal electron donor b is present, the molar ratio of said internal electron donor b to titanium in said solid catalyst component may be between 1000: 1 and 1: 1000.

The second application of the first aspect of the present invention relates to the use of said cyclotri veratrum hydrocarbon of formula (I) and its derivatives as external electron donor compounds in olefin polymerization catalyst systems, i.e. said cyclotri veratrum hydrocarbon of formula (I) and its derivatives are introduced into the polymerization reactor together with the solid catalyst component and the cocatalyst, with or without pre-contact between the solid catalyst component, the cocatalyst and said compound of formula (I).

According to the second application, there is no particular limitation on the specific type of the solid catalyst component combined with the cyclotris veratryl hydrocarbon of the formula (I) and its derivative and the preparation method thereof. For example, the solid catalyst component may be the solid catalyst component of the present invention, or any Ziegler-Natta type solid catalyst component known in the art to be useful in the polymerization of olefins. The present inventors have found that the olefin polymerization catalyst system shows good copolymerization performance when the cyclotri veratrum hydrocarbon and its derivatives are used as an external electron donor.

In some embodiments of the second application, the olefin polymerization catalyst comprises the reaction product of:

3) an external electron donor compound;

wherein the external electron donor compound comprises at least one of the above-described cyclotri-veratryl hydrocarbon and derivatives thereof.

In some embodiments, the solid catalyst component is the reaction product of a magnesium compound, a titanium compound, and optionally an internal electron donor compound.

The magnesium compound and the titanium compound are as described above.

According to the second application, the molar ratio of the external electron donor or the cyclotri-veratrum hydrocarbon and the derivative thereof to the titanium in the solid catalyst component is 0.05: 1-50: 1.

The optional internal electron donor compound may be any compound known in the art to be useful as an internal electron donor for solid catalyst components for olefin polymerization. For example, the optional internal electron donor compound may be selected from the internal electron donors b described in the first application. In addition, the internal electron donor compound also optionally comprises the cyclotri veratryl hydrocarbon and derivatives thereof (i.e. internal electron donor a). When the internal electron donor compound contains the cyclotri-veratrum hydrocarbon and the derivative thereof, the solid catalyst component is the solid catalyst component mentioned in the above-mentioned first application.

In some embodiments, the co-catalyst can be any organoaluminum compound known in the art to be useful as a co-catalyst for olefin polymerization catalysts. For example, the organoaluminum compound has the formula AlR'_dX’_3-dWherein R' is hydrogen or C_l-C₂₀A hydrocarbon group, X' is a halogen atom, 0<d≤3。C_l-C₂₀Hydrocarbyl radicals such as C_l-C₂₀Alkyl, aralkyl or aryl of (a). The organoaluminium compound is preferably selected from Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、AlH(CH₂CH₃)₂、Al[(CH₂)₅CH₃]₃，AlH(i-Bu)₂、AlCl(CH₂CH₃)₂、Al₂Cl₃(CH₂CH₃)₃、AlCl(CH₂CH₃)₂、AlCl₂(CH₂CH₃) More preferably from Al (CH)₂CH₃)₃，Al[(CH₂)₅CH₃]₃And/or Al (i-Bu)₃。

In some embodiments, the molar ratio of aluminum in component 2) to titanium in component 1) in the catalyst may be from 5: 1 to 500: 1, preferably from 20: 1 to 200: 1.

More details about the catalyst for olefin polymerization and the solid catalyst component therein will be described below.

In a second aspect, the present invention provides an olefin polymerization catalyst system comprising at least one cyclotri-veratrum hydrocarbon and derivatives thereof represented by formula (I) or formula (I') above as (I) an internal electron donor, (ii) an external electron donor, or (iii) both.

In a sub-aspect of the present invention, the present invention provides a solid catalyst component for olefin polymerization, comprising at least one cyclotri veratrum hydrocarbon represented by the above formula (I) or formula (I') and derivatives thereof as an internal electron donor compound.

In the present invention, there is no particular limitation in specific types of the solid catalyst component for olefin polymerization and the preparation method thereof, as long as the solid catalyst component comprises at least one cyclotri veratryl hydrocarbon represented by the above formula (I) or formula (I') and its derivatives as an internal electron donor compound. For example, the solid catalyst component may be any solid catalyst component known in the art for the polymerization of olefins, but comprising at least one cyclotri-veratryl hydrocarbon of formula (I) or (Γ) above and derivatives thereof, for example as a replacement or supplement to the internal electron donor contained therein.

In some embodiments, the solid catalyst component comprises magnesium, titanium, halogen, and an internal electron donor compound, wherein the internal electron donor compound comprises at least one compound represented by formula (I) or formula (Γ) above.

With respect to this solid catalyst component, in some preferred embodiments, the solid catalyst component comprises a titanium compound supported on a magnesium halide and the cyclotri-veratryl hydrocarbon and derivatives thereof. Preferably, the molar ratio of the cyclotri-veratrole hydrocarbon and the derivative thereof to the magnesium halide is 0.0005-0.1: 1, preferably 0.001-0.1: 1, more preferably 0.002-0.05: 1. Preferably, the titanium compound has the general formula Ti (OR)_nX’_4－nWherein R is C₁-C₈A hydrocarbon group, X' is a halogen atom, n is 0. ltoreq. n.ltoreq.4; more preferably, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, chlorotriethoxy titanium, dichlorodiethoxy titanium, tetrabutyl titanate and trichloromonoethoxy titanium.

In some embodiments, the solid catalyst component comprises the reaction product of: the catalyst comprises a magnesium halide alcoholate, a titanium compound, an internal electron donor compound and an optional organic aluminum compound, wherein the internal electron donor compound comprises at least one compound shown in the formula (I).

With respect to this solid catalyst component, in some preferred embodiments, the magnesium halide alcoholate has the formula MgX₂M (ROH), X is Cl, Br or I, preferably Cl; r is C₁-C₆Alkyl, m is from 0.5 to 4.0, preferably from 2.5 to 4.0.

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound has the formula Ti (OR)²)_nX² _4-nWherein R is²Is C₁-C₈A hydrocarbon group, preferably C₁-C₈An alkyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than or equal to 4; preferably, said titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃、Ti(OC₄H₉)₄At least one of (1).

With respect to this solid catalyst component, in some preferred embodiments, the organoaluminum compoundHas the general formula of AlR¹ _aX¹ _bH_cIn the formula, R¹Is C₁-C₁₄Hydrocarbyl radical, X¹Is a halogen atom, preferably fluorine, chlorine or bromine, a, b and c are each a number of 0 to 3, and a + b + c is 3.

With respect to this solid catalyst component, in some preferred embodiments, the at least one compound of formula (I) is present in an amount of at least 0.0005mol, preferably at least 0.001mol, preferably from 0.001 to 0.1mol, per mol of magnesium.

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound is used in an amount of 0.1 to 100mol, preferably 1 to 50mol, per mol of magnesium in the reaction for forming the solid catalyst component; the dosage of the organic aluminum compound is 0-5 mol; the cyclotri-veratrum hydrocarbon compound is used in an amount of at least 0.0005mol, preferably at least 0.001mol, preferably 0.001 to 0.1 mol.

In some embodiments, the solid catalyst component comprises the reaction product of: an alkoxy magnesium compound, a titanium compound and an internal electron donor compound, wherein the internal electron donor compound comprises at least one compound shown in the formula (I).

With respect to this solid catalyst component, in some preferred embodiments, the magnesium alkoxide compound has the formula Mg (OR)₃)_a(OR₄)_2-aWherein R is₃And R₄Same or different, each selected from substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy and hetero atom, and a is more than or equal to 0 and less than or equal to 2.

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound has the formula Ti (OR)_nX_4-nWherein R is C₁-C₈A hydrocarbon group, preferably C₁-C₈An alkyl group; x is halogen atom, n is more than or equal to 0 and less than or equal to 4; preferably, the titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃And Ti (OC)₄H₉)₄At least one of (1).

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound is used in an amount of 0.1 to 100mol, preferably 1 to 50mol, per mol of magnesium in the reaction for forming the solid catalyst component; the cyclotri-veratrum hydrocarbon compound is used in an amount of at least 0.0005mol, preferably at least 0.001mol, preferably 0.001 to 0.1 mol.

In some embodiments, the solid catalyst component comprises the reaction product of: the preparation method comprises the following steps of (1) carrying an ultrafine carrier with the particle size of 0.01-10 microns, magnesium halide, titanium halide and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor a and an internal electron donor b; the internal electron donor a is at least one compound shown in the formula (I); the internal electron donor b is selected from C₂-C₁₀Alkyl esters of saturated fatty carboxylic acids, C₇-C₁₀Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Fatty ethers, C₃-C₁₀Cyclic ether, C₃-C₁₀At least one of a saturated aliphatic ketone and a saturated aliphatic ketone,

with respect to this solid catalyst component, in some preferred embodiments, the magnesium halide is selected from MgCl₂、MgBr₂And MgI₂At least one of (1).

With respect to this solid catalyst component, in some preferred embodiments, the titanium halide is titanium tetrachloride and/or titanium trichloride.

With respect to this solid catalyst component, in some preferred embodiments, the ultrafine support is at least one selected from the group consisting of alumina, activated carbon, clay, silica, titania, polystyrene, and calcium carbonate.

With respect to this solid catalyst component, in some preferred embodiments, the molar ratio of the titanium halide to the internal electron donor a is from 5: 1 to 2000: 1, and the molar ratio of the titanium halide to the internal electron donor b is from 1: 1 to 1: 600.

With respect to this solid catalyst component, in some preferred embodiments, the internal electron donor b is at least one selected from the group consisting of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.

In some embodiments, the solid catalyst component comprises the reaction product of:

1) a magnesium-containing liquid component selected from at least one of the following components:

(ii) an alkyl magnesium or a solution thereof in a liquid hydrocarbon, said alkyl magnesium having the general formula MgR₁R₂Wherein R is₁And R₂Each independently selected from substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, halogen atom, alkoxy and heteroatom;

2) a titanium compound;

3) an internal electron donor compound comprising at least one compound represented by the above formula (I); and

optionally, 4) a precipitation aid selected from organic acid anhydrides and/or organosilicon compounds.

With respect to this solid catalyst component, in some preferred embodiments, the alkyl magnesium is selected from at least one of dimethyl magnesium, diethyl magnesium, n-butyl ethyl magnesium, di-n-butyl magnesium, butyl octyl magnesium.

With respect to this solid catalyst component, in some preferred embodiments, the magnesium dihalide or magnesium dihalide has one halogen atom in the formula replaced by a group R₃OR OR₄The substituted derivative is selected from MgCl₂、MgBr₂、MgI₂、MgCl(OCH₂CH₃)、MgCl(OBu)、CH₃MgCl and CH₃CH₂At least one of MgCl.

With respect to this solid catalyst component, in some preferred embodiments, the organophosphorus compound is selected from the group consisting of a hydrocarbyl or halohydrocarbyl ester of n-phosphoric acid, and a hydrocarbyl or halohydrocarbyl ester of phosphorous acid, preferably at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite, and di-n-butyl phosphite.

With respect to this solid catalyst component, in some preferred embodiments, the organic epoxide compound is selected from at least one of an oxide, glycidyl ether and internal ether of an aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin having 2 to 18 carbon atoms, preferably at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether.

With respect to this solid catalyst component, in some preferred embodiments, the alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, decanol, benzyl alcohol, and phenethyl alcohol.

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound has the formula Ti (OR)₆)_nX_4-nIn the formula, R₆Is C₁-C₈Of (2) a hydrocarbon groupX is a halogen atom, n is more than or equal to 0 and less than or equal to 3; the titanium compound is preferably chosen from TiCl₄、TiBr₄、TiI₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃、Ti(OC₂H₅)Br₃、Ti(OC₂H₅)₂Cl₂、Ti(OCH₃)₂Cl₂、Ti(OCH₃)₂I₂、Ti(OC₂H₅)₃Cl、Ti(OCH₃)₃Cl and Ti (OC)₂H₅)₃At least one of I.

With respect to this solid catalyst component, in some preferred embodiments, the organic anhydride compound is represented by formula (II):

wherein R is¹And R²Each independently selected from hydrogen and C₁-C₁₀The hydrocarbon group of (A), the R¹And R²Optionally joined into a ring.

With respect to this solid catalyst component, in some preferred embodiments, the organosilicon compound has the formula R³ _xR⁴ _ySi(OR⁵)_zIn the formula, R³And R⁴Each independently selected from C₁-C₁₀And halogen, R⁵Is C₁-C₁₀X, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x + y + z is 4.

With respect to this solid catalyst component, in some preferred embodiments, the titanium compound is used in an amount of 0.5 to 120mol, preferably 1 to 50mol, per mol of magnesium in the reaction for forming the solid catalyst component; the cyclotri-veratrole hydrocarbon and the derivative thereof are used in an amount of 0.0005 to 1mol, preferably 0.001 to 0.05 mol.

As mentioned above, there is no particular limitation on the method for preparing the solid catalyst component of the present invention. In principle, any method known in the art for preparing solid catalyst components may be used to prepare the solid catalyst component of the present invention, except that the cyclotri-veratryl hydrocarbon of formula (I) and its derivatives are introduced as internal electron donor before, during or after the formation of the solid catalyst component.

In some embodiments, the solid catalyst component may be prepared according to a process comprising the steps of:

(1) preparation of mother liquor

Mixing magnesium halide, titanium halide and an internal electron donor compound, and reacting at 0-90 ℃ for 0.5-5 hours to obtain mother liquor;

(2) mother liquor for preparing superfine carrier blend

Mixing the mother liquor obtained in the step (1) with the superfine carrier at 0-90 ℃ and stirring for 0.5-3 hours to obtain mother liquor mixed with the superfine carrier;

(3) spray forming

The mother liquor mixed with the superfine carrier is sprayed and dried to prepare a solid catalyst component,

wherein the content of the superfine carrier in the mother solution blended with the superfine carrier is 3-50 wt%, preferably 10-30 wt%.

In other embodiments, the solid catalyst component may be prepared according to a process comprising the steps of:

1) dissolving magnesium halide in a solvent system containing an organic epoxy compound, an organic phosphorus compound, organic alcohol and an internal electron donor a to form a uniform solution;

2) the solution is contacted with a titanium compound and organosiloxane at low temperature for reaction, and solid particles containing magnesium, titanium, halogen and alkoxy are gradually separated out in the gradual heating process;

3) the liquid is removed from the reaction mixture and the residual solids are washed, for example with an inert solvent, to give the solid catalyst component.

1) in the presence of an inert solvent, contacting and reacting magnesium halide with an alcohol compound and an internal electron donor compound;

2) then adding an organic silicon compound for contact and reaction;

3) contacting and reacting the system in the step 2) with a titanium compound;

4) the liquid is removed from the reaction mixture and the residual solids are washed to obtain the solid catalyst component.

1) dispersing a magnesium halide alcoholate in an inert solvent to obtain a suspension;

2) contacting and reacting the suspension with an organoaluminum compound and an internal electron donor compound, then removing the liquid from the reaction mixture, and washing the residual solid;

3) contacting and reacting the solid obtained in step 2) with a titanium compound in the presence of an inert solvent, then removing the liquid from the reaction mixture, and washing the residual solid to obtain the solid catalyst component.

Further details of this process can be found in CN102807638A, the entire disclosure of which is incorporated herein by reference.

1) dispersing an alkoxy magnesium compound in an inert solvent to obtain a suspension;

2) contacting and reacting the suspension with a titanium compound, then removing liquid from the reaction mixture, and washing the residual solids;

3) contacting the precipitate obtained in the step 2) with a titanium compound and an internal electron donor compound in the presence of an inert solvent for reaction, then removing liquid from the reaction mixture, and washing the residual solid to obtain the solid catalyst component.

The above-described methods are known per se, but additionally or alternatively the cyclotri-veratrum hydrocarbon and derivatives thereof are used as internal electron donor/internal electron donor a. The other reactants involved in these processes are as described previously. In general, the cyclotri-veratrum hydrocarbon and its derivatives may be introduced into the solid catalyst component before, during or after the formation of the particles of the solid catalyst component, preferably before or during the formation of the particles of the solid catalyst component.

In some specific embodiments, the solid catalyst component may be prepared according to a process comprising the steps of:

2) contacting and reacting the suspension with a titanium compound, cyclotri-veratrolene and derivatives thereof, then removing the liquid from the reaction mixture and washing the residual solids;

3) contacting and reacting the mixture obtained in step 2) with a titanium compound, optionally in the presence of an inert solvent, followed by removing the liquid from the reaction mixture and washing the residual solids to obtain the solid catalyst component.

In other specific embodiments, the solid catalyst component may be prepared according to a process comprising the steps of:

3) contacting and reacting the mixture obtained in step 2) with a titanium compound, cyclotri-veratrole hydrocarbon and derivatives thereof, optionally in the presence of an inert solvent, followed by removing the liquid from the reaction mixture and washing the residual solids to obtain the solid catalyst component.

(1) preparation of mother liquor

Mixing magnesium halide, titanium halide, an internal electron donor a and an internal electron donor b, and reacting at 0-90 ℃ for 0.5-5 hours to obtain mother liquor;

(2) mother liquor for preparing superfine carrier blend

Mixing the mother liquor obtained in the step (1) with an ultrafine carrier at 0-90 ℃ and stirring for 0.5-3 hours to obtain an ultrafine carrier blended mother liquor, wherein the content of the ultrafine carrier in the ultrafine carrier blended mother liquor is preferably 3-50 wt%, more preferably 10-30 wt%;

(3) spray forming

And (3) carrying out spray drying on the mother liquor mixed with the superfine carrier to prepare the solid catalyst component.

In another sub-aspect of the second aspect of the invention, the invention provides an olefin polymerisation catalyst comprising the reaction product of:

1) the solid catalyst component of the present invention described above;

3) optionally an external electron donor component.

In this regard, in some embodiments, the optional external electron donor component can comprise any compound known in the art to be useful as an external electron donor for olefin polymer catalyst systems, such as organosilanes, and/or comprise at least one of the cyclotri-veratrum hydrocarbons and derivatives thereof described above.

In this sub-aspect, there are no strict limitations on the co-catalyst, and those known in the art to be useful as co-catalysts for olefin polymerization catalyst systems may be used. In some embodiments, the cocatalyst is of the formula AlR³ _aX³ _bH_cAn organoaluminum compound of (A), wherein R is³Is C₁-C₂₀A hydrocarbyl group; x³Is a halogen atom, preferably Cl, Br or I; a. b and c are each a number from 0 to 3, and a + b + c is 3. Examples of the organoaluminum compound include Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、Al[(CH₂)₅CH₃]₃、AlH(CH₂CH₃)₂、AlCl(CH₂CH₃)₂、AlH(i-Bu)₂、AlCl_1.5(CH₂CH₃)_1.5、AlCl(CH₂CH₃)₂And AlCl₂(CH₂CH₃). Preferably, the co-catalyst is a trialkylaluminum, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.

In some preferred embodiments, the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 5: 1 to 500: 1, preferably 20: 1 to 200: 1.

2) cocatalysts, such as organoaluminum compounds; and

3) an external electron donor compound;

wherein the external electron donor compound comprises at least one of the above cyclotri veratrum hydrocarbon and its derivatives.

According to this sub-aspect, the solid catalyst component comprising magnesium, titanium, halogen and optionally an internal electron donor compound may be any ziegler-natta type solid catalyst component for olefin polymerization known in the art.

In some embodiments, the solid catalyst component comprises a titanium compound having at least one Ti-halogen bond supported on a magnesium halide. Preferably, the titanium compound is selected from titanium trihalides and/OR compounds of formula Ti (OR)²)_nX² _4－nWherein R is²Is C₁-C₈A hydrocarbon group, preferably C₁-C₈An alkyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than 4; preferably, the titanium compound is selected from TiCl₃、TiCl₄、TiBr₄、Ti(OC₂H₅)Cl₃、Ti(OC₂H₅)₂Cl₂And Ti (OC)₂H₅)₃At least one of Cl.

The cocatalyst is as described above.

In addition to the cyclotri veratrum hydrocarbon and its derivatives, the external electron donor component may further comprise any compound known in the art to be useful as an external electron donor for olefin polymerization catalyst systems, such as organosilanes. This is within the scope of the invention.

With respect to the solid catalyst component, the optional internal electron donor compound is present in an amount of 0 to 1mol per mol of magnesium.

In this sub-aspect, the molar ratio of the aluminium of the co-catalyst, such as an organoaluminium compound, to the titanium of the solid catalyst component is from 5: 1 to 500: 1, preferably from 20: 1 to 200: 1.

In this sub-aspect, the molar ratio of the external electron donor compound to the titanium of the solid catalyst component is from 0.05: 1 to 50: 1.

According to this sub-aspect, in some embodiments, the catalyst system comprises the reaction product of:

1) a solid catalyst component comprising the reaction product of: a magnesium halide alcoholate, a titanium compound, an optional internal electron donor compound and an optional second organic aluminum compound, wherein the general formula of the second organic aluminum compound is AlR³ _aX³ _bH_cIn the formula, R³Is C₁-C₁₄A hydrocarbyl group; x³Is a halogen atom, preferably Cl, Br or I; a. b and c are each a number from 0 to 3, and a + b + c is 3;

2) a cocatalyst selected from a first organoaluminum compound having the general formula AlR¹ _dX¹ _3-dIn the formula, R¹Is hydrogen or C_l-C₂₀Hydrocarbyl radical, X¹Is halogen atom, d is more than 0 and less than or equal to 3;

3) an external electron donor compound comprising at least one of the above cyclotri veratryl hydrocarbon and derivatives thereof.

Preferably, the magnesium halide alcoholate has the formula MgX₂M (ROH), wherein X is Cl, Br or I, preferably Cl; r is C₁-C₆Alkyl, preferably C₁-C₄An alkyl group; m is 0.5 to 4.0, preferably 2.5 to 4.0.

Preferably, the titanium compound has the formula Ti (OR)²)_nX² ₄－_nWherein R is²Is C₁-C₈A hydrocarbon group, preferably C₁-C₈An alkyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than or equal to 4; preferably, the titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃And Ti (OC)₄H₉)₄At least one of (1).

Preferably, the second organoaluminium compound is selected from Al (CH)₂CH₃)₃、Al(i-Bu)₃And Al (n-C)₆H₁₃)₃At least one of (1).

Preferably, the titanium compound is used in an amount of 1 to 50mol per mol of magnesium in the reaction to form the solid catalyst component; the dosage of the internal electron donor compound is 0-1 mol; the second organoaluminum compound is used in an amount of 0 to 100 mol.

Preferably, the molar ratio of aluminum in the first organoaluminum compound to titanium in the solid catalyst component is 5: 1 to 500: 1, preferably 20: 1 to 200: 1.

Preferably, the molar ratio of the external electron donor compound to the titanium in the solid catalyst component is from 0.05: 1 to 50: 1.

According to this sub-aspect, in some embodiments, the present invention provides an olefin polymerization catalyst comprising the reaction product of:

1) a solid catalyst component comprising the reaction product of: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound;

2) a cocatalyst;

Preferably, the magnesium alkoxide compound has the formula Mg (OR)₃)_a(OR₄)_2-a，R₃And R₄Each independently is substituted or unsubstituted C₁-C₁₀The substituent group of the alkyl is hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom, and a is more than or equal to 0 and less than or equal to 2.

Preferably, the titanium compound is used in an amount of 0.1 to 15mol per mol of magnesium in the reaction to form the solid catalyst component; the dosage of the internal electron donor compound is 0-0.1 mol.

The cocatalyst is as described above.

Preferably, the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 5: 1 to 500: 1, preferably 20: 1 to 200: 1.

1) a solid catalyst component comprising the reaction product of: superfine carrier, magnesium halide, titanium halide, internal electron donor b and optional internal electron donor a;

wherein the internal electron donor b is selected from C₂-C₁₀Alkyl esters of saturated fatty carboxylic acids, C₇-C₁₀Alkyl ester of aromatic carboxylic acid, C₂-C₁₀Fatty ethers, C₃-C₁₀Cyclic ethers and C₃-C₁₀At least one of saturated aliphatic ketones; and

wherein the optional internal electron donor a is selected from at least one of cyclotri veratrohydrocarbon shown in formula (I) and derivatives thereof;

2) a cocatalyst;

Preferably, the ultrafine support is selected from at least one of alumina, activated carbon, clay, silica, titania, magnesia, zirconia, polystyrene, and calcium carbonate; the particle size of the superfine carrier is 0.01-10 mu m;

preferably, the magnesium halide is selected from MgCl₂、MgBr₂And MgI₂At least one of (a).

Preferably, the titanium halide is TiCl₃And/or TiCl₄。

Preferably, in the solid catalyst component, the molar ratio of the titanium halide to the magnesium halide is 1: 20 to 1: 2, and the molar ratio of the titanium halide to the internal electron donor b is 1: 1 to 1: 600.

According to this sub-aspect, in some embodiments, the present invention provides an olefin polymerisation catalyst comprising the reaction product of:

1) a solid catalyst component comprising the reaction product of: the composite material comprises a magnesium-containing liquid component, a titanium compound, an optional internal electron donor compound and an optional auxiliary precipitator, wherein the auxiliary precipitator is selected from organic acid anhydride compounds and/or organosilicon compounds;

2) a cocatalyst;

Preferably, the liquid magnesium-containing component is selected from at least one of the following components:

and (2) component A: an alkyl magnesium compound having the general formula MgR₃R₄；

And (B) component: reaction products of magnesium compounds with organic phosphorus compounds, organic epoxy compounds and optionally alcohol compounds of the general formula R₇OH；

And (3) component C: a reaction product of a magnesium compound and an alcohol compound, wherein the alcohol compound has a general formula of R₇OH；

Wherein the magnesium compound has the general formula of MgX³ _mR³ _2-mIn the formula X³Is halogen, R³is-R₅OR-OR₆M is 1 or 2; r₃、R₄、R₅、R₆And R₇Identical or different, are each substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, halogen atom, alkoxy or heteroatom.

Preferably, the titanium compound has the formula Ti (OR)²)_nX² _4－nWherein R is²Is C₁-C₈A hydrocarbon group, preferably C₁-C₈An alkyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than or equal to 4; preferably, the titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃And Ti (OC)₄H₉)Cl₃At least one of (1).

Preferably, the organic acid anhydride compound is at least one selected from compounds represented by formula (II):

wherein R is⁴And R⁵Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl or C₆-C₁₀Aromatic hydrocarbon radical, R⁴And R⁵Optionally interconnected to form a ring.

Preferably, the organosilicon compound has a general formula of R⁶ _xR⁷ _ySi(OR⁸)_zIn the formula, R⁶And R⁷Each independently is C₁-C₁₀Hydrocarbyl or halogen, R⁸Is C₁-C₁₀A hydrocarbon group, x, y and z are integers, 0. ltoreq. x.ltoreq.2, 0. ltoreq. y.ltoreq.2, 0. ltoreq. z.ltoreq.4, and x + y + z is 4.

Preferably, the titanium compound is used in an amount of 0.5 to 120mol, preferably 1 to 50mol, per mol of magnesium in the reaction to form the solid catalyst component; the dosage of the internal electron donor compound is 0-0.1mol, preferably 0-0.05 mol; the dosage of the precipitation aid is 0-1mol, preferably 0-0.7 mol.

In relation to this sub-aspect, in the embodiment in which the solid catalyst component is the solid catalyst component of the present invention described previously, the preparation of the solid catalyst component is as described previously.

In this sub-aspect, in the embodiment in which the solid catalyst component is not the solid catalyst component of the present invention described above but is a solid catalyst component known in the art, the preparation of the solid catalyst component can be carried out according to various methods taught in the prior art.

The solid catalyst component, the cocatalyst and the external electron donor compound of the catalyst system are introduced together into a polymerization reactor to cause polymerization of olefins, with or without pre-contact between the solid catalyst component, the cocatalyst and the compound of formula (I).

The olefin polymerization catalyst system containing the cyclotri-veratrum hydrocarbon and the derivative thereof as the internal electron donor and/or the external electron donor is suitable for homopolymerization or copolymerization of olefin. Examples of such olefins include, but are not limited to: ethylene, propylene, butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene.

Accordingly, in a third aspect, the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction. A fourth aspect of the present invention provides an olefin polymerization process comprising: contacting an olefin monomer and optionally a comonomer with the olefin polymerization catalyst described above under polymerization conditions to form a polyolefin product, and recovering the polyolefin product.

The olefin polymerization process and the polymerization conditions employed therein are known per se. For example, the olefin polymerization reaction can be carried out in liquid phase or gas phase, or also in a mode of operation in which liquid phase and gas phase polymerization stages are combined. The polymerization temperature may be from 0 to 150 ℃ and preferably from 60 to 90 ℃.

Examples of liquid phase polymerization media include: and inert solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.

In addition, hydrogen gas may be used as a molecular weight modifier in order to adjust the molecular weight of the final polymer.

In some embodiments, the olefin polymerization process comprises contacting ethylene and an optional comonomer, such as a C3-C12 alpha-olefin, with the olefin polymerization catalyst described above under polymerization conditions to form a polyethylene product, and recovering the polyethylene product.

In other embodiments, the olefin polymerization process comprises contacting propylene and an optional comonomer, such as ethylene or a C4-C12 alpha-olefin, with the olefin polymerization catalyst described above under polymerization conditions to form a polypropylene product, and recovering the polypropylene product.

Detailed Description

The present invention is illustrated by the following examples, which should not be construed as limiting the scope of the invention.

In the following examples and comparative examples, unless otherwise indicated, the temperature values refer to the values in ° c and the pressures are gauge pressures.

Test method

1. The relative weight percentage of titanium element in the solid catalyst component is as follows: spectrophotometry is adopted. Other compositions of the solid catalyst component: using liquid nuclear magnetism¹H-NMR。

2. Polymer Melt Index (MI): determined according to ASTM D1238-99, load 2.16Kg (or 21.6Kg), 190 ℃.

3. Content of copolymerized units in the polymer powder: using liquid nuclear magnetism¹³C-NMR determination.

4. Weight content of hexane extractables in polymer powder: m g of the dried powder was taken and placed in a Soxhlet extractor and Soxhlet extracted for 4 hours with hexane. And completely drying the powder subjected to Soxhlet extraction to obtain n g of powder. The hexane extractables are then (m-n)/m x 100% by mass.

5. Melting content of polymer powder: and (3) carrying out three-stage test on the sample by adopting a Perkin Elmer DSC8500 differential scanning calorimeter, wherein the test atmosphere is nitrogen.

A first stage: heating the sample from 0 ℃ to 160 ℃, keeping the temperature at 160 ℃ for 5min to eliminate the thermal history, wherein the heating rate is 10K/min;

and a second stage: cooling the sample from 160 ℃ to 0 ℃ at a cooling rate of 10K/min;

a third stage: the sample is heated from 0 ℃ to 160 ℃, and the heating rate is 10K/min.

And selecting a melting box of the third section of temperature rise curve as a test result.

Both the melting content and the bulk density of the sample depend on the crystallinity. For the polymer powder obtained under the same copolymerization conditions (e.g. same comonomer type/concentration, reaction temperature/pressure/time, hydrogen to ethylene ratio, etc.), the bulk density is lower for the one with lower melt content.

Preparation examples 1 to 4 are provided to illustrate the preparation method of cyclotri veratryl hydrocarbon and its derivatives.

Preparation example 1

1, 2-o-dimethyl ether (1.0g) was added dropwise to a mixture of aqueous formaldehyde (4mL, 38%), chloroform (0.1mL) and concentrated hydrochloric acid (6mL) under ice-bath conditions to react, after 30 minutes the solution became pasty, and the reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was filtered to collect a solid, the solid was washed with ice water, and the solid was completely dried to obtain 0.5g of compound a.

Preparation example 2

3-methoxy-4-bromo-benzyl alcohol (3.6g) was dissolved in 30mL of methanol under ice-bath conditions. 15mL of 65% perchloric acid was added dropwise to the above solution with stirring in an ice bath. The reaction solution was stirred in an ice bath for 18h under nitrogen blanket. To the reaction solution, 30mL of water was slowly added, followed by extraction of the organic phase with dichloromethane. The organic phase was washed carefully with aqueous sodium hydroxide and then with deionized water. After drying the organic phase, it was evaporated thoroughly under reduced pressure and purified by column chromatography to give 0.8g of compound M.

Preparation example 3

1, 2-o-phenylether (3.3g) and trioxymethylene (0.63g) were dissolved in dry dichloromethane (30mL), and the solution was stirred under ice bath. Boron trifluoride diethyl etherate (4.25g) was slowly added dropwise to the above solution, and after the addition was completed, the ice-water bath was removed. The reaction solution was stirred at room temperature for 3 hours, followed by TLC (thin layer chromatography) until the reaction was complete, and the reaction was stopped. The reaction solution was washed with water 3 times, the organic layer was separated using a separatory funnel, and the organic solvent was completely evaporated under reduced pressure to give an oil. A small amount of acetone is added to dissolve the oily matter, a large amount of methanol is added to the oily matter, and the oily matter is stood in a refrigerator to separate out white solid. The white solid was filtered off with suction and dried thoroughly to give 1.5g of compound B.

Preparation example 4

3-methoxy-4-ethoxy-benzyl alcohol (3g) was dissolved in 30mL of methanol under nitrogen and ice bath conditions. To the above solution, 15mL of 65% perchloric acid was added dropwise with stirring in an ice bath, and then the reaction solution was stirred for 18 hours (ice bath). To the reaction solution, 30mL of water was slowly added, followed by extraction of the organic phase with dichloromethane. The organic phase was washed with aqueous sodium hydroxide and then with deionized water. After drying the organic phase, it was evaporated thoroughly under reduced pressure and purified by column chromatography to give 1.0g of compound F.

Examples 1-5 are presented to illustrate the use of cyclotri veratrum hydrocarbons and their derivatives as internal electron donors in ethylene polymerization catalysts.

Example 1

(1) Preparation of solid catalyst component a

6.0g of MgCl spherical carrier is sequentially added into a reaction kettle which is fully replaced by high-purity nitrogen₂·2.6C₂H₅OH, 120mL of toluene, and cooling the reaction mixture to-10 ℃ with stirring. To the above reaction mixture was added dropwise 50mL of a hexane solution of triethylaluminum (1.0M), and then 0.15g of Compound A was added, followed by warming to 50 ℃ and maintaining the temperature at 50 ℃ for 3 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction and the precipitate was washed several times with toluene and then hexane. To the reaction kettle containing the solid particles was added 120mL of hexane, and the reaction mixture was cooled to 0 ℃ with stirring. 6mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, and then the temperature was raised to 60 ℃ and held at 60 ℃ for 2 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly.The supernatant was removed by suction, and the precipitate was washed twice with hexane, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component a with good fluidity, the composition of which is shown in table 1.

(2) Homopolymerization reaction

Polymerization with a low hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 75 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 1.03MPa (gauge pressure). The polymerization was maintained at 85 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain a total pressure of 1.03MPa (gauge pressure), and the polymerization results are shown in Table 2.

② polymerization with high hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 75 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.68MPa, and ethylene is introduced to ensure that the total pressure in the kettle reaches 1.03 MPa. The polymerization was maintained at 85 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain a total pressure of 1.03MPa, and the polymerization results are shown in Table 2.

Comparative examples 1 to 1

(1) Preparation of solid catalyst component D1-1

6.0g of MgCl spherical carrier is sequentially added into a reaction kettle which is fully replaced by high-purity nitrogen₂·2.6C₂H₅OH, 120mL of toluene, and cooling the reaction mixture to-10 ℃ with stirring. To the above reaction mixture was added dropwise 50mL of a hexane solution of triethylaluminum (1.0M), followed by warming to 50 ℃ and holding at 50 ℃ for 3 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction and the precipitate was washed several times with toluene and then hexane. To contain solid particles120mL of hexane was added to the reaction kettle, and the reaction mixture was cooled to 0 ℃ with stirring. 6mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, and then the temperature was raised to 60 ℃ and held at 60 ℃ for 2 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed twice with hexane, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component D1-1 with good flowability, the composition of which is shown in Table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component D1-1 prepared in comparative example 1-1 was used, and the polymerization results are shown in Table 2.

Comparative examples 1 to 2

(1) Preparation of solid catalyst component D1-2

6.0g of MgCl spherical carrier is sequentially added into a reaction kettle which is fully replaced by high-purity nitrogen₂·2.6C₂H₅OH, 120mL of toluene, and cooling the reaction mixture to-10 ℃ with stirring. To the above reaction mixture was added dropwise 50mL of a hexane solution of triethylaluminum (1.0M), 1.5mL of ethyl benzoate was further added, and then the temperature was raised to 50 ℃ and maintained at 50 ℃ for 3 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction and the precipitate was washed several times with toluene and then hexane. To the reaction kettle containing the solid particles was added 120mL of hexane, and the reaction mixture was cooled to 0 ℃ with stirring. 6mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, and then the temperature was raised to 60 ℃ and held at 60 ℃ for 2 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed twice with hexane, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component D1-2 having good flowability, the composition of which is shown in Table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component D1-2 prepared in comparative example 1-2 was used, and the polymerization results were shown in Table 2.

TABLE 2 polymerization results

As shown in Table 2, when the cyclotriveratrum hydrocarbon derivative was introduced into the solid catalyst component a (example 1), the activity of the catalyst under high hydrogen-ethylene ratio polymerization conditions was significantly higher than that of the comparative example, and the melt index of the polymerization powder was also significantly higher than that of the comparative example.

Furthermore, as shown in Table 2, when the cyclotri-veratrum hydrocarbon derivative was introduced as an internal electron donor into the solid catalyst component, the activity of the catalyst under the polymerization conditions of low hydrogen-ethylene ratio and the melt index of the polymerization powder were also improved.

Example 2

(1) Preparation of solid catalyst component b

4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate, 4.4mL of ethanol, and 0.2g of Compound A were sequentially added to a reaction vessel which had been fully purged with high-purity nitrogen. The reaction mixture was warmed to 70 ℃ with stirring and thermostated at 70 ℃ for 2 hours. The reaction mixture was cooled to-10 ℃ and 70mL of titanium tetrachloride was slowly added dropwise, followed by 5mL of tetraethoxysilane, and then gradually heated to 85 ℃ and kept at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid catalyst component b with good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

Polymerization with low hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 70 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain a total pressure of 0.73MPa (gauge pressure), and the polymerization results are shown in Table 3.

② polymerization with high hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 70 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.60MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 1.00MPa (gauge pressure). The polymerization was maintained at 90 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain a total pressure of 1.00MPa (gauge pressure), and the polymerization results are shown in Table 3.

(3) Ethylene-butene copolymerization

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. Raising the temperature of the kettle to 70 ℃ under stirring, introducing hydrogen to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and introducing ethylene/butylene mixed gas (the molar ratio is 0.75: 0.25) to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 0.5 hour, during which time the above ethylene/butene mixed gas was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 4.

(4) Ethylene-hexene copolymerization

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The kettle was warmed to 70 ℃ with stirring, 20ml of hexene were added, hydrogen was introduced to bring the pressure in the kettle to 0.28MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the kettle to 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 0.5 hour, during which time ethylene was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 5.

Comparative example 2

(1) Preparation of solid catalyst component D2

4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were sequentially added to a reaction vessel which had been sufficiently replaced with high-purity nitrogen. The reaction mixture was warmed to 70 ℃ with stirring and thermostated at 70 ℃ for 2 hours. The reaction mixture was cooled to-10 ℃ and 70mL of titanium tetrachloride was slowly added dropwise, followed by 5mL of tetraethoxysilane, and then gradually heated to 85 ℃ and kept at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blow-dried with high-purity nitrogen to obtain a solid catalyst component D2 having good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 2, except that the solid catalyst component D2 prepared in comparative example 2 was used, and the polymerization results were shown in Table 3.

(3) Ethylene-butene copolymerization

The polymerization procedure was the same as in example 2, except that the solid catalyst component D2 prepared in comparative example 2 was used, and the polymerization results were shown in Table 4.

(4) Ethylene-hexene copolymerization

The polymerization procedure was the same as in example 2, except that the solid catalyst component D2 prepared in comparative example 2 was used, and the polymerization results were shown in Table 5.

TABLE 3 homopolymerization results

As shown in Table 3, when the cyclotriveratrum hydrocarbon derivative was introduced into the solid catalyst component b (example 2), the activity of the catalyst under high hydrogen-ethylene ratio polymerization conditions was significantly higher than that of the comparative example, and the melt index of the polymerization powder was also significantly higher than that of the comparative example.

As also shown in Table 3, when the cyclotri-veratrum hydrocarbon derivative is introduced as an internal electron donor into the solid catalyst component, the activity of the catalyst under low hydrogen-ethylene ratio polymerization conditions and the melt index of the polymerization powder can be improved.

TABLE 4 ethylene-butene copolymerization results (powder)

	Melting box	Content of copolymerized units
			Example 2	139J/g	3.0mol％
Comparative example 2	146J/g	4.2mol％

As shown in Table 4, when the cyclotriveratrum hydrocarbon derivative was introduced into the solid catalyst component b of example 2, the polymerization product thereof could achieve a lower melting content (i.e., a lower density) under ethylene/butene copolymerization conditions with a lower content of copolymerized units. This indicates that the distribution of copolymerized units is more uniform in the polymerized product of example 2.

TABLE 5 ethylene-hexene copolymerization results (powder)

	Melting box	Content of copolymerized units	Hexane extractables
				Example 2	176J/g	0.75mol％	3.9wt％
Comparative example 2	179J/g	0.68mol％	4.1wt％

As shown in Table 5, when the cyclotriveratrum hydrocarbon derivative was introduced into the solid catalyst component b of example 2, the melting content of the polymerization product was lower (i.e., lower density) under ethylene/hexene copolymerization conditions. In addition, in the case of the polymerization product of example 2 having a high content of copolymerized units, the hexane extractables were rather lower. This shows that the copolymerized units are distributed more uniformly in the polymerized product of example 2.

Example 3

(1) Preparation of solid catalyst component c

4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were sequentially added to a reaction vessel which had been sufficiently replaced with high-purity nitrogen. The reaction mixture was warmed to 70 ℃ with stirring and thermostated at 70 ℃ for 2 hours. The reaction mixture was cooled to-10 ℃ and 65mL of titanium tetrachloride was slowly added dropwise, followed by 4mL of tetraethoxysilane, and then gradually heated to 85 ℃ and kept at 85 ℃ for 1 hour. 0.2g of Compound B was added to the reaction vessel, and the temperature was maintained at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid catalyst component c with good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

Polymerization with low hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 70 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 6.

② polymerization with high hydrogen/ethylene ratio

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 70 ℃ under stirring, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.58MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 2 hours, during which time ethylene was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 6.

Comparative example 3

(1) Preparation of solid catalyst component D3

4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were sequentially added to a reaction vessel which had been sufficiently replaced with high-purity nitrogen. The reaction mixture was warmed to 70 ℃ with stirring and thermostated at 70 ℃ for 2 hours. The reaction mixture was cooled to-10 ℃ and 65mL of titanium tetrachloride was slowly added dropwise, followed by 4mL of tetraethoxysilane, and then gradually heated to 85 ℃ and kept at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blow-dried with high-purity nitrogen to obtain a solid catalyst component D3 having good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 3, except that the solid catalyst component D3 prepared in comparative example 3 was used, and the polymerization results were shown in Table 6.

TABLE 6 homopolymerization results

As shown in Table 6, when the cycloveratrum hydrocarbon derivative was introduced into the solid catalyst component c of example 3, the activity of the catalyst under the high hydrogen-ethylene ratio polymerization conditions and the melt index of the polymerization powder were significantly higher than those of the comparative example.

Example 4a

(1) Preparation of solid catalyst component d1

4.0 g of magnesium chloride, 80mL of toluene, 3.5mL of epichlorohydrin and 13mL of tri-n-butyl phosphate were sequentially added to a reaction vessel which had been fully replaced with high-purity nitrogen. The reaction mixture was warmed to 60 ℃ with stirring and thermostated at 60 ℃ for 2 hours. 1.4g of phthalic anhydride was added to the reaction vessel, and the temperature was maintained at 60 ℃ for 1 hour. The reaction mixture was cooled to-30 ℃ and 60mL of titanium tetrachloride was slowly added dropwise, followed by gradual heating to 85 ℃ and constant temperature at 85 ℃ for 1 hour. 0.15g of Compound A was added to the reaction vessel, and the temperature was maintained at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to give a solid catalyst component d1 with good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component d1 prepared in example 4a was used, and the polymerization results are shown in Table 7.

Example 4b

(1) Preparation of solid catalyst component d2

4.0 g of magnesium chloride, 80mL of toluene, 3.5mL of epichlorohydrin and 13mL of tri-n-butyl phosphate were sequentially added to a reaction vessel which had been fully replaced with high-purity nitrogen. The reaction mixture was warmed to 60 ℃ with stirring and thermostated at 60 ℃ for 2 hours. 1.4g of phthalic anhydride was added to the reaction vessel, and the temperature was maintained at 60 ℃ for 1 hour. The reaction mixture was cooled to-30 ℃ and 60mL of titanium tetrachloride was slowly added dropwise, followed by gradual heating to 85 ℃ and constant temperature at 85 ℃ for 1 hour. 0.1g of Compound B was added to the reaction vessel, and the temperature was maintained at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to give a solid catalyst component d2 with good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component d2 prepared in example 4b was used, and the polymerization results are shown in Table 7.

(3) Copolymerization reaction

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of the solid catalyst component (containing 0.6mg of titanium) prepared by the above-mentioned method. The temperature of the kettle is raised to 75 ℃ under stirring, 20ml of hexene is added, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and ethylene is introduced to ensure that the total pressure in the kettle reaches 1.03MPa (gauge pressure). The polymerization was maintained at 85 ℃ for 0.5 hour, during which time ethylene was continuously introduced into the reactor to maintain the total pressure at 1.03MPa (gauge pressure), and the polymerization results are shown in Table 8.

Comparative example 4

(1) Preparation of solid catalyst component D4

4.0 g of magnesium chloride, 80mL of toluene, 3.5mL of epichlorohydrin and 13mL of tri-n-butyl phosphate were sequentially added to a reaction vessel which had been fully replaced with high-purity nitrogen. The reaction mixture was warmed to 60 ℃ with stirring and thermostated at 60 ℃ for 2 hours. 1.4g of phthalic anhydride was added to the reaction vessel, and the temperature was maintained at 60 ℃ for 1 hour. The reaction mixture was cooled to-30 ℃ and 60mL of titanium tetrachloride was slowly added dropwise, followed by gradual heating to 85 ℃ and constant temperature at 85 ℃ for 1 hour. The stirring of the reactor was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blow-dried with high-purity nitrogen to obtain a solid catalyst component D4 having good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component D4 prepared in comparative example 4 was used, and the polymerization results were shown in Table 7.

(3) Copolymerization reaction

The polymerization procedure was the same as in example 4b, except that the solid catalyst component D4 prepared in comparative example 4 was used, and the polymerization results were shown in Table 8.

TABLE 7 homopolymerization results

As shown in Table 7, when the cycloveratrole hydrocarbon derivative was introduced into the solid catalyst component d1/d2 of example 4a/4b, the activity of the catalyst under high hydrogen-ethylene ratio polymerization conditions and the melt index of the polymerization powder were higher than those of the comparative example.

TABLE 8 ethylene-hexene copolymerization results (powder)

	Melting box
		Example 4b	181J/g
Comparative example 4	184J/g

As shown in Table 8, when a cycloveratrum hydrocarbon derivative was introduced into the solid catalyst component d2 of example 4b, the melting content of the polymerization product was lower (i.e., lower density) than that of comparative example 4 under ethylene/hexene copolymerization conditions.

Example 5

(1) Preparation of solid catalyst component e

In a reaction vessel fully substituted by high-purity nitrogen, 2.0 g of magnesium chloride, 80mL of toluene, 2mL of epichlorohydrin and 6mL of tri-n-butyl phosphate were sequentially added. The reaction mixture was warmed to 60 ℃ with stirring and thermostated at 60 ℃ for 2 hours. The reaction mixture was cooled to-30 ℃ and 30mL of titanium tetrachloride was slowly added dropwise, followed by gradual heating to 85 ℃ and constant temperature at 85 ℃ for 1 hour. 0.1g of Compound A was added to the reaction vessel, and the temperature was maintained at 85 ℃ for 1 hour. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid catalyst component e with good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component e prepared in example 5 was used, and the polymerization results were shown in Table 9.

(3) Ethylene-butene copolymerization

The polymerization procedure was the same as in example 2, except that the solid catalyst component e prepared in example 5 was used, and the polymerization results were as shown in Table 10.

Comparative example 5

(1) Preparation of solid catalyst component D5

In a reaction vessel fully substituted by high-purity nitrogen, 2.0 g of magnesium chloride, 80mL of toluene, 2mL of epichlorohydrin and 6mL of tri-n-butyl phosphate were sequentially added. The reaction mixture was warmed to 60 ℃ with stirring and thermostated at 60 ℃ for 2 hours. The reaction mixture was cooled to-30 ℃ and 30mL of titanium tetrachloride was slowly added dropwise, followed by gradual heating to 85 ℃ and constant temperature at 85 ℃ for 1 hour. The stirring of the reactor was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blow-dried with high-purity nitrogen to obtain a solid catalyst component D5 having good flowability, the composition of which is shown in table 1.

(2) Homopolymerization reaction

The polymerization procedure was the same as in example 1, except that the solid catalyst component D5 prepared in comparative example 5 was used, and the polymerization results were shown in Table 9.

3) Ethylene-butene copolymerization

The polymerization procedure was the same as in example 2, except that the solid catalyst component D5 prepared in comparative example 5 was used, and the polymerization results were as shown in Table 10.

TABLE 9 homopolymerization results

As shown in Table 9, when the cycloveratrum hydrocarbon derivative was introduced into the solid catalyst component e of example 5, the activity of the catalyst under high hydrogen-ethylene ratio polymerization conditions was higher than that of the comparative example, and the melt index of the polymerization powder was significantly higher than that of the comparative example.

TABLE 10 ethylene-butene copolymerization results (powder)

	Melting box	Hexane extractables
			Example 5	127J/g	26.4mol％
Comparative example 5	139J/g	35.4mol％

As shown in Table 10, when the cycloveratryl hydrocarbon derivative was introduced into the solid catalyst component e of example 5, not only was the polymerization product able to achieve a lower melting content (i.e., lower density) but the hexane extractables of the polymerization product was rather lower under ethylene/butene copolymerization conditions. This indicates that the copolymerized units are more uniformly distributed in the polymerized product of example 5.

Examples 6-8 are presented to illustrate the use of cyclotri veratrum hydrocarbons and their derivatives as external electron donors in ethylene polymerization catalysts.

Example 6

(1) Preparation of solid catalyst component f

The procedure for preparing the solid catalyst component was the same as in comparative example 4.

(2) Ethylene-butene copolymerization

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of 25mg of the solid catalyst component prepared by the above-mentioned method and 40mg of Compound A. Raising the temperature of the kettle to 70 ℃ under stirring, introducing hydrogen to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and introducing ethylene/butylene mixed gas (the molar ratio is 0.935: 0.065) to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 0.5 hour, during which time the above ethylene/butene mixed gas was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results were shown in Table 11.

Comparative example 6

(1) Preparation of solid catalyst component f

(2) Ethylene-butene copolymerization

The polymerization procedure was the same as in example 6, except that the compound A was omitted. The polymerization results are shown in Table 11.

TABLE 11 ethylene-butene copolymerization results (powder)

	Melting box	Content of copolymerized units
			Example 6	166J/g	1.0mol％
Comparative example 6	170J/g	1.1mol％

As shown in Table 11, when the cyclotriveratrum hydrocarbon derivative was introduced into the polymerization system of example 6 as an external electron donor, the polymerization product could reach a lower melting content (i.e., a lower density) with a lower content of copolymerized units under the ethylene/butene copolymerization conditions. This indicates that the copolymerized units are more uniformly distributed in the polymerized product of example 6.

Example 7

(1) Preparation of solid catalyst component g

The procedure for preparing the solid catalyst component was the same as in comparative example 2.

(2) Ethylene-butene copolymerization

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of 24mg of the solid catalyst component prepared by the above-mentioned method and 42mg of Compound A. Raising the temperature of the kettle to 70 ℃ under stirring, introducing hydrogen to ensure that the pressure in the kettle reaches 0.28MPa (gauge pressure), and introducing ethylene/butylene mixed gas (the molar ratio is 0.75: 0.25) to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 0.5 hour, during which time the above ethylene/butene mixed gas was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 12.

Comparative example 7

(1) Preparation of solid catalyst component g

(2) Ethylene-butene copolymerization

The polymerization procedure was the same as in example 7, except that 42mg of ethyl benzoate was used instead of said 42mg of Compound A. The polymerization results are shown in Table 12.

TABLE 12 ethylene-butene copolymerization results (powder)

	Melting box	Content of copolymerized units
			Example 7	153J/g	1.9mol％
Comparative example 7	165J/g	1.4mol％

As shown in Table 12, when a cyclotriveratrum hydrocarbon derivative was introduced as an external electron donor into the polymerization system of example 7, the polymerization product was able to achieve a lower melting content (i.e., a lower density) relative to the ethyl benzoate used in comparative example 7.

Example 8

(1) Preparation of solid catalyst component h

4.0 g of magnesium chloride, 50mL of toluene, 3.3mL of epichlorohydrin, 8mL of tri-n-butyl phosphate and 4.4mL of ethanol were sequentially added to a reaction vessel which had been sufficiently replaced with high-purity nitrogen. The reaction mixture was warmed to 68 ℃ with stirring and thermostatted at 68 ℃ for 2 hours. The reaction mixture was cooled to-10 ℃ and 65mL of titanium tetrachloride was slowly added dropwise, followed by 6mL of tetraethoxysilane, and then gradually heated to 85 ℃ and kept at 85 ℃ for 2 hours. The stirring of the reaction vessel was stopped, the reaction mixture was allowed to stand and the solid particles precipitated quickly. The supernatant was removed by suction, and the precipitate was washed with toluene and hexane several times, transferred to a sintered glass funnel with hexane, and blown dry with high purity nitrogen to obtain a solid catalyst component h with good flowability, the composition of which is shown in table 1.

(2) Ethylene-hexene copolymerization

A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, and then 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, followed by addition of 11mg of the solid catalyst component prepared by the above-mentioned method and 11mg of Compound A. The kettle was warmed to 70 ℃ with stirring, 20ml of hexene were added, hydrogen was introduced to bring the pressure in the kettle to 0.28MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the kettle to 0.73MPa (gauge pressure). The polymerization was maintained at 80 ℃ for 0.5 hour, during which time ethylene was continuously introduced into the reactor to maintain the total pressure at 0.73MPa (gauge pressure), and the polymerization results are shown in Table 13.

Comparative example 8

(1) Preparation of solid catalyst component h

The procedure for the preparation of the solid catalyst component was the same as in example 8.

(2) Ethylene-hexene copolymerization

The polymerization procedure was the same as in example 8, except that the compound A was omitted. The polymerization results are shown in Table 13.

TABLE 13 ethylene-hexene copolymerization results (powder)

	Melting box	Hexane extractables
			Example 8	186J/g	1.1wt％
Comparative example 8	186J/g	2.4wt％

As shown in Table 13, when a cyclotriveratrum hydrocarbon derivative was introduced as an external electron donor into the polymerization system of example 8 under ethylene/hexene copolymerization conditions, the fusion content of the polymerization powder was not decreased as compared with that of comparative example 8, but hexane extractables were significantly decreased. This property is advantageous for stable industrial production.

Examples 9-10 are provided to illustrate the use of cyclotri veratrum hydrocarbons and derivatives thereof as internal electron donors in propylene polymerization catalysts.

Example 9(1) preparation of component i of the solid catalyst

To a 300mL glass reaction flask with stirring which had been sufficiently purged with high-purity nitrogen gas were added 50mL of titanium tetrachloride and 40mL of hexane in this order, and the mixture was cooled to-20 ℃ with stirring. To the above solution was added 9g of spherical magnesium chloride alcoholate (MgCl)₂·2.6C₂H₅OH, synthesized with magnesium dichloride and ethanol according to the method disclosed in CN 1330086A). The reaction mixture was slowly warmed up in stages with stirring, 0.25mmol of compound A, 5mmol of Diisobutylphthalate (DIBP) and 20ml of toluene were added during warming up, then the temperature was raised to 110 ℃ and the temperature was maintained at 110 ℃ for 0.5 h. The flask was stopped and the reaction mixture was allowed to stand and the solid phase precipitated quickly. The supernatant was removed by suction, and 80mL of titanium tetrachloride was added to the solid phase in the reaction flask and treated twice. The solid phase is then washed five times with hexane and dried under vacuum to give the spherical solid catalyst component i whose composition is given in Table 1.

(2) Propylene polymerization

A5L autoclave was purged with a stream of nitrogen. Then, under the protection of a nitrogen stream, 0.25mmol of triethylaluminum, 0.01mmol of Cyclohexylmethyldimethoxysilane (CHMMS), 10mL of anhydrous hexane and 10mg of spherical catalyst component i were added to the reaction vessel. The autoclave was closed and 1.2NL (normal volume) of hydrogen and 2.3L of liquid propylene were added. The temperature of the reaction vessel was raised to 70 ℃ and polymerization was carried out for 1.0 hour. The polymerization results are shown in Table 14.

Comparative example 9:

(1) preparation of component D9 of the solid catalyst

The spherical solid catalyst component D9 was prepared by the procedure described in example 9, but the compound a was omitted. The composition is shown in Table 1.

(2) Propylene polymerization

The polymerization procedure was the same as in example 9, except that the solid catalyst component D9 prepared in comparative example 9 was used, and the polymerization results were as shown in Table 14.

TABLE 14 propylene polymerization results

As shown in Table 14, when the cyclotriveratrum hydrocarbon derivative was introduced into the solid catalyst component i of example 9, the polymerization activity of the catalyst was significantly improved and the isotacticity of the polymerized powder material satisfied the application requirements.

Example 10

(1) Preparation of component j of the solid catalyst

To a 300mL glass reaction flask with stirring which had been sufficiently purged with high-purity nitrogen gas were added 50mL of titanium tetrachloride and 40mL of hexane in this order, and the mixture was cooled to-20 ℃ with stirring. To the above solution was added 9g of spherical magnesium chloride alcoholate (MgCl)₂·2.6C2H₅OH, synthesized with magnesium dichloride and ethanol according to the method disclosed in CN 1330086A). The reaction mixture was slowly warmed up in stages with stirring, 0.25mmol of the compound A, 5mmol of di-n-butyl phthalate (DNBP) and 20ml of toluene were added during warming, then the temperature was raised to 110 ℃ and maintained at 110 ℃ for 0.5 h. The flask was stopped and the reaction mixture was allowed to stand and the solid phase precipitated quickly. The supernatant was removed by suction, and 80mL of titanium tetrachloride was added to the solid phase in the reaction flask and treated twice. The solid phase is then washed five times with hexane and dried under vacuum to give the spherical solid catalyst component j, the composition of which is shown in Table 1.

(2) Propylene polymerization

The polymerization procedure was the same as in example 9, except that the solid catalyst component j prepared in example 10 was used, and the polymerization results were shown in Table 15.

Comparative example 10:

(1) preparation of component D10 of the solid catalyst

The spherical solid catalyst component D10 was prepared by the procedure described in example 10, but the compound a was omitted. The composition is shown in Table 1.

(2) Propylene polymerization

The polymerization procedure was the same as in example 9, except that the solid catalyst component D10 prepared in comparative example 10 was used, and the polymerization results were as shown in Table 15.

TABLE 15 propylene polymerization results

As shown in Table 15, when the Tricycloveratrum hydrocarbon derivative was introduced into the solid catalyst component j of example 10, the polymerization activity of the catalyst was significantly improved, and the isotacticity of the polymerized powder satisfied the application requirements.

Example 11 is provided to illustrate the use of cyclotri veratrum hydrocarbons and derivatives thereof as external electron donors in propylene polymerization catalysts.

Example 11

In this example, propylene polymerization was carried out using an NDQ catalyst from Odak catalyst, a petrochemical company, wherein compound A was used as an external electron donor.

Propylene polymerization procedure

In a 5L autoclave, purged with a stream of nitrogen, 0.25mmol triethylaluminum, 0.01mmol external electron donor (Compound A), 10mL anhydrous hexane, and 10mg of the catalyst NDQ were added to the autoclave under the protection of the stream of nitrogen. The autoclave was closed and 1.2NL (normal volume) of hydrogen and 2.3L of liquid propylene were added. The temperature of the reaction vessel was raised to 70 ℃ and polymerization was carried out for 1.0 hour. The polymerization results are shown in Table 16.

Comparative example 11

In this comparative example, propylene polymerization was carried out using an NDQ catalyst from Odada catalyst, a petrochemical company, wherein Compound A was not used as an external electron donor.

Propylene polymerization procedure

In a 5L autoclave, purged with a stream of nitrogen, 0.25mmol triethylaluminum, 10mL anhydrous hexane, and 10mg of the catalyst NDQ-were added to the autoclave under the protection of a stream of nitrogen. The autoclave was closed and 1.2NL (normal volume) of hydrogen and 2.3L of liquid propylene were added. The temperature of the reaction vessel was raised to 70 ℃ and polymerization was carried out for 1.0 hour. The polymerization results are shown in Table 16.

TABLE 16 propylene polymerization results

Examples	External electron donor	Activity (kgPP/gCat)	Isotacticity (wt%)
				Example 11	Compound A	53	97.9
Comparative example 11	--	60	95.1

As can be seen from Table 16, the catalyst polymerization system provided by the present invention can be applied to propylene polymerization, and the isotacticity of the polymer obtained in example 11 is improved as compared with that of comparative example 11 in which compound A is not added.

TABLE 1 composition of the solid catalyst component

While illustrative embodiments of the invention have been particularly described, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains. The invention has been described above in connection with a number of embodiments and specific examples. Many variations will be apparent to those of ordinary skill in the art in view of the above detailed description. All such variations are within the full intended scope of the appended claims.

In the present disclosure, when a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that we also contemplate the same composition, element, or group of elements, wherein the composition, element, or group of elements is preceded by the transitional phrase "consisting essentially of …," "consisting of …," "selected from the group consisting of …," or "is," and vice versa.

Claims

1. A Ziegler-Natta type catalyst system for the polymerization of olefins comprising at least one compound of formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) both,

wherein M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆' each is independently selected from hydrogen, hydroxy, halogen atom, -R₁OR-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁-C₁₀Hydrocarbon radicals or radicals selected from hydroxy, halogen, and C₁-C₁₀C substituted by substituents of alkoxy₁-C₁₀A hydrocarbyl group; wherein when M is₁-M₆And M₁’-M₆Any two adjacent groups on the same phenyl ring in' are each independently selected from R₁and-OR₂When the two adjacent groups are optionally linked to form a ring,

provided that M is₁、M₂、M₃、M₄、M₅、M₆、M₁’、M₂’、M₃’、M₄’、M₅’、M₆' not both are hydrogen.

2. The catalyst system of claim 1, wherein the compound of formula (I) is selected from those of formula (Γ):

wherein M is₁、M₂、M₃、M₄、M₅And M₆Each independently selected from hydrogen, hydroxy, halogen, -R₁and-OR₂Wherein R is₁And R₂Each independently of the other being unsubstituted C₁-C₁₀Hydrocarbon radicals or radicals selected from hydroxy, halogen, and C₁-C₁₀C substituted by substituents of alkoxy₁-C₁₀A hydrocarbyl group, provided that when two groups adjacent to each other on the same phenyl ring are M₁And M₂Or M₃And M₄Or M₅And M₆Each independently selected from-R₁and-OR₂When said two adjacent groups are optionally linked to form a ring, and with the proviso that M is₁、M₂、M₃、M₄、M₅And M₆Not hydrogen at the same time.

3. The catalyst system as claimed in claim 2, wherein, in the formula (I'), M₁、M₂、M₃、M₄、M₅And M₆Each independently selected from hydroxy, halogen, -R₁OR-OR₂Wherein R is₁And R₂Each independently selected from unsubstituted or halogen-substituted C₁-C₁₀A hydrocarbyl group.

4. The catalyst system of claim 1, wherein the at least one compound of formula (i) is selected from the group consisting of:

Compound B: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H

Compound C: m is a group of₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound H: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝OCH₂CH₂CH₂CH₃，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

A compound L: m₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝Cl，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound M: m is a group of₁＝M₃＝M₅＝OCH₃，M₂＝M₄＝M₆＝Br，M₁’＝M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

A compound S: m₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝Cl，M₂’＝M₃’＝M₄’＝M₅’＝M₆’＝H；

Compound V: m is a group of₁＝M₂＝M₃＝M₄＝M₅＝M₆＝OCH₃，M₁’＝M₃’＝M₆’＝Cl，M₂’＝M₄’＝M₅’＝H。

5. A solid catalyst component for the polymerization of olefins comprising magnesium, titanium, halogen and an internal electron donor compound, wherein said internal electron donor compound comprises at least one compound of formula (i) as described in any one of claims 1 to 4.

6. The solid catalyst component according to claim 5 comprising at least one titanium compound and said at least one compound of formula (I) supported on a magnesium halide.

7. The solid catalyst component according to claim 5 or 6 in which the molar ratio of the at least one compound of formula (I) to magnesium is from 0.0005 to 0.1: 1.

8. The solid catalyst component according to claim 5 or 6 in which the molar ratio of the at least one compound of formula (I) to magnesium is from 0.001 to 0.1: 1.

9. The solid catalyst component according to claim 5 or 6 in which the molar ratio of the at least one compound of formula (I) to magnesium is between 0.002 and 0.05: 1.

10. The solid catalyst component according to claim 6 in which the at least one titanium compound is chosen from titanium trichloride and compounds having the general formula Ti (OR)_nX’_4－nWherein R is C₁-C₈A hydrocarbon group, X' is a halogen atom, and n is 0 to 4.

11. The solid catalyst component according to claim 6 in which the at least one titanium compound is chosen from titanium trichloride, titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, chlorotriethoxy titanium, dichlorodiethoxy titanium, tetrabutyl titanate and trichloromonoethoxy titanium.

12. The solid catalyst component of claim 5 comprising the reaction product of:

1) a magnesium halide alcoholate;

2) a titanium compound;

3) an internal electron donor compound; and

4) optionally, an organoaluminum compound,

wherein the internal electron donor compound comprises the at least one compound represented by formula (I).

13. The solid catalyst component of claim 12 having at least one of the following characteristics:

-said organoaluminium compound has the general formula AlR¹ _aX¹ _bH_cIn the formula, R¹Is C₁-C₁₄Hydrocarbyl radical, X¹Is a halogen atom, a, b, c are each a number from 0 to 3, and a + b + c is 3;

-the at least one compound of formula (i) is present in an amount of at least 0.0005mol per mol of magnesium;

-said magnesium halide alcoholate has the general formula MgX₂M (ROH), wherein X is Cl, Br or I; r is C₁-C₆Alkyl, m is 0.5-4.0;

-said titanium compound having the general formula Ti (OR)²)_nX² _4-nWherein R is²Is C₁-C₈A hydrocarbyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than or equal to 4;

-said titanium compound is used in an amount ranging from 0.1 to 100mol and said organoaluminum compound is used in an amount ranging from 0 to 5mol per mol of magnesium in the reaction for forming said solid catalyst component.

14. The solid catalyst component of claim 12 having at least one of the following characteristics:

-the at least one compound of formula (i) is present in an amount of 0.001 to 0.1mol per mol of magnesium;

-said magnesium halide alcoholate has the general formula MgX₂M (ROH), wherein X is Cl, Br or I; r is C₁-C₆Alkyl, m is 2.5-4.0;

-said titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃、Ti(OC₄H₉)₄And mixtures thereof;

-the titanium compound is used in an amount of 1 to 50mol and the organoaluminum compound is used in an amount of 0 to 5mol per mol of magnesium in the reaction for forming the solid catalyst component.

15. The solid catalyst component of claim 5 comprising the reaction product of:

1) an alkoxy magnesium compound;

2) a titanium compound; and

3) an internal electron donor compound;

16. The solid catalyst component of claim 15 having at least one of the following characteristics:

-said alkaneThe magnesium oxo compound has the general formula of Mg (OR)₃)_a(OR₄)_2-aWherein R is₃And R₄Each independently selected from unsubstituted C₁-C₁₀Or C substituted by a substituent selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a hetero atom₁-C₁₀And 0. ltoreq. a.ltoreq.2;

-said titanium compound having the formula Ti (OR)_nX_4-nWherein R is C₁-C₈A hydrocarbyl group; x is halogen atom, n is more than or equal to 0 and less than or equal to 4;

-said titanium compound is used in an amount ranging from 0.1 to 100mol per mol of magnesium in the reaction for forming said solid catalyst component;

-the solid catalyst component is prepared by a process comprising the steps of: dispersing the alkoxy magnesium compound in an inert solvent to obtain a suspension; contacting said suspension with a titanium compound and said at least one compound of formula (i) to obtain a contact product; and further reacting the contact product with a titanium compound to obtain the solid catalyst component,

alternatively, the solid catalyst component is prepared by a process comprising the steps of: dispersing the alkoxy magnesium compound in an inert solvent to obtain a suspension; contacting said suspension with a titanium compound to obtain a contact product; and further reacting the contact product with a titanium compound and the at least one compound represented by the formula (I) to obtain the solid catalyst component.

17. The solid catalyst component of claim 15 having at least one of the following characteristics:

-the content of said at least one compound of formula (i) is in the range of 0.001-0.1mol per mol of magnesium;

-said titanium compound is used in an amount of 1 to 50mol per mol of magnesium in the reaction to form said solid catalyst component.

18. The solid catalyst component of claim 5 comprising the reaction product of:

1) superfine carrier with particle size of 0.01-10 micron;

2) a magnesium halide;

3) a titanium halide; and

4) an internal electron donor compound comprising an internal electron donor a and an internal electron donor b,

wherein the internal electron donor a is the at least one compound shown in the formula (I), and the internal electron donor b is at least one selected from alkyl esters of C2-C10 saturated aliphatic carboxylic acids, alkyl esters of C7-C10 aromatic carboxylic acids, C2-C10 aliphatic ethers, C3-C10 cyclic ethers and C3-C10 saturated aliphatic ketones; and is

Wherein the molar ratio of the titanium halide to the internal electron donor a is 5: 1-2000: 1, and the molar ratio of the titanium halide to the internal electron donor b is 1: 1-1: 600.

19. The solid catalyst component of claim 18 having at least one of the following characteristics:

-said internal electron donor b is at least one selected from methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone;

-said magnesium halide is selected from MgCl₂、MgBr₂And MgI₂At least one of;

-the titanium halide is at least one selected from titanium tetrachloride and titanium trichloride;

-the ultrafine support is at least one selected from the group consisting of alumina, activated carbon, clay, silica, titania, polystyrene and calcium carbonate;

-the solid catalyst component is prepared by a process comprising the steps of: mixing the magnesium halide, the titanium halide, the internal electron donor a and the internal electron donor b, and reacting at 0-90 ℃ for 0.5-5 hours to obtain mother liquor; mixing the mother liquor and the superfine carrier at 0-90 ℃ and stirring for 0.5-3 hours to obtain mother liquor blended with the superfine carrier; and spray-drying the mother liquor blended with the superfine carrier to obtain the solid catalyst component, wherein the content of the superfine carrier in the mother liquor blended with the superfine carrier is 3-50 wt%.

20. The solid catalyst component of claim 5 comprising the reaction product of:

(ii) an alkyl magnesium or a solution thereof in a liquid hydrocarbon, said alkyl magnesium having the general formula MgR₁R₂，R₁And R₂Each independently selected from substituted or unsubstituted C₁-C₁₀The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, halogen atom, alkoxy and heteroatom;

wherein R is₃、R₄And R₅Each independently selected from substituted or unsubstituted C₁-C₁₀A hydrocarbon group, the substituent being selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a halogen atom, an alkoxy group and a hetero atom;

2) a titanium compound;

3) an internal electron donor compound; and

4) optionally, a precipitation aid selected from organic acid anhydride compounds and/or organosilicon compounds,

21. The solid catalyst component of claim 20 having at least one of the following characteristics:

-said alkyl magnesium is at least one selected from the group consisting of dimethyl magnesium, diethyl magnesium, n-butyl ethyl magnesium, di-n-butyl magnesium, butyl octyl magnesium;

-said magnesium dihalide or magnesium dihalide of the formula in which one halogen atom is replaced by a group R₃OR OR₄The substituted derivative is selected from MgCl₂、MgBr₂、MgI₂、MgCl(OCH₂CH₃)、MgCl(OBu)、CH₃MgCl and CH₃CH₂At least one of MgCl;

-said organophosphorus compound is selected from the group consisting of hydrocarbyl esters and halogenated hydrocarbyl esters of orthophosphoric acid, and hydrocarbyl esters and halogenated hydrocarbyl esters of phosphorous acid;

-the organic epoxy compound is at least one selected from the group consisting of oxides, glycidyl ethers and internal ethers of aliphatic olefins, diolefins or halogenated aliphatic olefins or diolefins having 2 to 18 carbon atoms;

-the alcohol compound is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, decanol, benzyl alcohol and phenethyl alcohol;

-said titanium compound having the general formula Ti (OR)₆)_nX_4-nIn the formula, R₆Is C₁-C₈X is a halogen atom, n is 0. ltoreq. n.ltoreq.3;

-the organic acid anhydride compound is represented by formula (II):

wherein R is¹And R²Each independently selected from hydrogen or C₁-C₁₀The hydrocarbon group of (A), the R¹And R²Optionally linked to form a ring;

-said organic phaseThe silicon compound has the general formula R³ _xR⁴ _ySi(OR⁵)_zIn the formula, R³And R⁴Each independently selected from C₁-C₁₀A hydrocarbon group or a halogen atom, R⁵Is C₁-C₁₀The alkyl is a positive integer, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x + y + z is 4;

-said titanium compound is used in an amount ranging from 0.5 to 120 moles per mole of magnesium in the reaction to form said solid catalyst component; the at least one compound of formula (I) is used in an amount of 0.0005 to 1 mol.

22. The solid catalyst component of claim 20 having at least one of the following characteristics:

-the organophosphorus compound is at least one selected from the group consisting of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite;

-the organic epoxy compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether;

-said titanium compound is chosen from TiCl₄、TiBr₄、TiI₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃、Ti(OC₂H₅)Br₃、Ti(OC₂H₅)₂Cl₂、Ti(OCH₃)₂Cl₂、Ti(OCH₃)₂I₂、Ti(OC₂H₅)₃Cl、Ti(OCH₃)₃Cl and Ti (OC)₂H₅)₃At least one of I;

-said titanium compound is used in an amount ranging from 1 to 50 moles per mole of magnesium in the reaction to form said solid catalyst component; the at least one compound of formula (I) is used in an amount of 0.001 to 1 mol.

23. A catalyst system for olefin polymerization comprising the reaction product of:

1) the solid catalyst component of any one of claims 5 to 22;

2) a cocatalyst which is at least one compound of the general formula AlR¹ _dX¹ _3-dWherein R is¹Is hydrogen or C_l-C₂₀Hydrocarbyl radical, X¹Is a halogen atom, and d is more than 0 and less than or equal to 3; and

3) optionally an external electron donor compound.

24. The catalyst system of claim 23, wherein the cocatalyst is selected from Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、Al[(CH₂)₅CH₃]₃、AlH(CH₂CH₃)₂、AlCl(CH₂CH₃)₂、AlH(i-Bu)₂、AlCl_1.5(CH₂CH₃)_1.5、AlCl(CH₂CH₃)₂And AlCl₂(CH₂CH₃) At least one of (1).

25. The catalyst system of any one of claims 23-24, wherein the molar ratio of aluminum in the co-catalyst to titanium in the solid catalyst component is 5: 1 to 500: 1, or 20: 1 to 200: 1.

26. The catalyst system of claim 25, wherein the molar ratio of aluminum in the co-catalyst to titanium in the solid catalyst component is 20: 1 to 200: 1.

27. A catalyst system for olefin polymerization comprising the reaction product of:

3) an external electron donor compound comprising at least one compound of formula (i) as defined in any one of claims 1 to 4.

28. The catalyst system of claim 27, wherein the cocatalyst is selected from Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、Al[(CH₂)₅CH₃]₃、AlH(CH₂CH₃)₂、AlCl(CH₂CH₃)₂、AlH(i-Bu)₂、AlCl_1.5(CH₂CH₃)_1.5、AlCl(CH₂CH₃)₂And AlCl₂(CH₂CH₃) At least one of (1).

29. The catalyst system of claim 27, wherein the solid catalyst component comprises at least one titanium compound having at least one Ti-halogen bond supported on a magnesium halide.

30. The catalyst system of claim 29, wherein the at least one titanium compound is selected from the group consisting of titanium trihalides and compounds of the formula Ti (OR)²)_nX² _4－nWherein R is²Is C₁-C₈A hydrocarbyl group; x²Is Cl, Br or I, and n is more than or equal to 0 and less than 4.

31. The catalyst system of claim 29, wherein the at least one titanium compound is selected from the group consisting of TiCl₃、TiCl₄、TiBr₄、Ti(OC₂H₅)Cl₃、Ti(OC₂H₅)₂Cl₂And Ti (OC)₂H₅)₃Cl。

32. The catalyst system of claim 27, having at least one of the following characteristics:

-the molar ratio of aluminium in the cocatalyst to titanium in the solid catalyst component is from 5: 1 to 500: 1;

-the molar ratio of the external electron donor compound to the titanium of the solid catalyst component is between 0.05: 1 and 50: 1.

33. The catalyst system of claim 27, wherein the solid catalyst component comprises the reaction product of: a magnesium halide alcoholate, a titanium compound, an optional internal electron donor compound and an optional second organic aluminum compound, wherein the general formula of the second organic aluminum compound is AlR³ _aX³ _bH_cIn the formula, R³Is C₁-C₁₄A hydrocarbyl group; x³Is a halogen atom; a. b and c are each a number from 0 to 3, and a + b + c is 3.

34. The catalyst system of claim 33, having at least one of the following characteristics:

-said magnesium halide alcoholate has the general formula MgX₂M (ROH), wherein X is Cl, Br or I; r is C₁-C₆An alkyl group; m is 0.5-4.0;

-said titanium compound having the general formula Ti (OR)²)_nX² _4－nWherein R is²Is C₁-C₈A hydrocarbyl group; x²Is Cl, Br or I, n is more than or equal to 0 and less than or equal to 4;

-said second organoaluminium compound is selected from Al (CH)₂CH₃)₃、Al(i-Bu)₃、Al(n-C₆H₁₃)₃And mixtures thereof;

-said titanium compound is used in an amount ranging from 1 to 50 moles per mole of magnesium in the reaction to form said solid catalyst component; the dosage of the internal electron donor compound is 0-1 mol; the second organoaluminum compound is used in an amount of 0 to 100 mol.

35. The catalyst system of claim 27, wherein the solid catalyst component comprises the reaction product of: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound.

36. The catalyst system of claim 35, having at least one of the following characteristics:

-said magnesium alkoxide compound having the general formula Mg (OR)₃)_a(OR₄)_2-aWherein R is₃And R₄Each independently of the other being unsubstituted C₁-C₁₀Alkyl or C substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde, carboxyl, acyl, halogen, alkoxy and hetero atom₁-C₁₀Alkyl, and 0. ltoreq. a.ltoreq.2;

-said titanium compound is used in an amount of 0.1 to 15mol per mol of magnesium in the reaction to form said solid catalyst component; and the amount of the internal electron donor compound is 0 to 0.1 mol.

37. The catalyst system of claim 27, wherein the solid catalyst component comprises the reaction product of: ultrafine carrier, magnesium halide, titanium halide, internal electron donor b and optional internal electron donor a, wherein the internal electron donor b is selected from C₂-C₁₀Alkyl esters of saturated fatty carboxylic acids, C₇-C₁₀Alkyl ester of aromatic carboxylic acid, C₂-C₁₀Fatty ethers, C₃-C₁₀Cyclic ethers and C₃-C₁₀At least one saturated aliphatic ketone, and wherein said optional internal electron donor a is at least one compound of formula (I).

38. The catalyst system of claim 37, having at least one of the following characteristics:

-the ultrafine support is selected from the group consisting of alumina, activated carbon, clay, silica, titania, polystyrene, calcium carbonate and mixtures thereof, and the particle size of the ultrafine support is 0.01 to 10 μm;

-said magnesium halide is selected from MgCl₂、MgBr₂、MgI₂And mixtures thereof;

-said titanium halide is TiCl₃And/or TiCl₄；

-the solid catalyst component is prepared by a process comprising the steps of: combining magnesium halide, titanium halide, internal electron donor b and optional internal electron donor a to prepare mother liquor; mixing a superfine carrier with the mother liquor to prepare slurry liquid; and spray drying the slurry to obtain the solid catalyst component, wherein the content of the superfine carrier in the slurry is 3-50 wt%;

-the molar ratio of the titanium halide to the magnesium halide is from 1: 20 to 1: 2;

-the molar ratio of the titanium halide to the internal electron donor b is from 1: 1 to 1: 600.

39. The catalyst system of claim 27, wherein the solid catalyst component comprises the reaction product of: the titanium-containing composite material comprises a magnesium-containing liquid component, a titanium compound, an optional internal electron donor compound and an optional auxiliary precipitator, wherein the auxiliary precipitator is selected from organic acid anhydride compounds and organic silicon compounds.

40. The catalyst system of claim 39, having at least one of the following characteristics:

-the liquid magnesium-containing component is selected from at least one of the following components:

And (3) component C: a reaction product of a magnesium compound and an alcohol compound, the alcohol compound having the general formula R₇OH，

Wherein the magnesium compound has the general formula of MgX³ _mR³ _2-mIn the formula X³Is halogen, R³is-R₅OR-OR₆M is 1 or 2; r₃、R₄、R₅、R₆And R₇Each independently of the other being unsubstituted C₁-C₁₀Hydrocarbon group or C substituted by a substituent selected from the group consisting of hydroxyl group, amino group, aldehyde group, carboxyl group, halogen atom, alkoxy group and hetero atom₁-C₁₀A hydrocarbyl group;

-said general formula is R₇The alcohol compound of OH is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, decanol, benzyl alcohol and phenethyl alcohol;

-the organic acid anhydride compound is at least one compound selected from the group consisting of compounds represented by the formula (II),

wherein R is⁴And R⁵Each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl or C₆-C₁₀Aromatic hydrocarbon radical, R⁴And R⁵Optionally linked to form a ring;

-said organosilicon compound has the general formula R⁶ _xR⁷ _ySi(OR⁸)_zIn the formula, R⁶And R⁷Each independently is C₁-C₁₀Hydrocarbyl or halogen, R⁸Is C₁-C₁₀A hydrocarbyl group, x, y and z are integers, x is 0. ltoreq. 2, y is 0. ltoreq. 2, z is 0. ltoreq. 4, and x + y + z is 4;

-said titanium compound is used in an amount ranging from 0.5 to 120 moles per mole of magnesium in the reaction to form said solid catalyst component; the dosage of the internal electron donor compound is 0-0.1 mol; the dosage of the precipitation assistant is 0-1 mol.

41. The catalyst system of claim 39, having at least one of the following characteristics:

-the organophosphorus compound is at least one selected from triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite;

-said titanium compound is selected from TiCl₄、Ti(OC₂H₅)Cl₃、Ti(OCH₃)Cl₃、Ti(OC₄H₉)Cl₃And mixtures thereof;

-said titanium compound is used in an amount ranging from 1 to 50 moles per mole of magnesium in the reaction to form said solid catalyst component; the dosage of the internal electron donor compound is 0-0.05 mol; the dosage of the precipitation aid is 0-0.7 mol.

42. An olefin polymerization process, comprising: contacting an olefin monomer and optionally a comonomer with the catalyst system of any of claims 1-4 and 23-41 under polymerization conditions to form a polyolefin product, and recovering the polyolefin product.